"presentations" "Title(English)","Title(Japanese)","Presenter(s)(English)","Presenter(s)(Japanese)","Conference name(English)","Conference name(Japanese)","Presentation date","Invited talk","Language","Presentation type","Organizer(English)","Organizer(Japanese)","Venue(English)","Venue(Japanese)","URL","Description(English)","Description(Japanese)" "Advanced DFT-MD Study on Ion Transport in Solid Electrolyte: Grain Boundary and Ion Correlation","Advanced DFT-MD Study on Ion Transport in Solid Electrolyte: Grain Boundary and Ion Correlation","館山 佳尚","館山 佳尚","IUMRS-ICAM & ICMAT 2023","IUMRS-ICAM & ICMAT 2023","2023-06-26","","eng","oral_presentation","","","","","","In this work, using DFT-based molecular dynamics (DFT-MD) with a sufficient predictability, we have addressed the elucidation of microscopic ion behaviors in the SEs. First targets are the electronic states and the ionic conductivities around the GBs of the garnet-type Li7La3Zr2O7 SE as well as the dopant effects (Al, Ga, Nb, Ta). ","" "Evaluation of Battery Positive-electrode Performance with Ab-inito Simultaneous Calculations of the Electronic and Ionic Conductivities","Evaluation of Battery Positive-electrode Performance with Ab-inito Simultaneous Calculations of the Electronic and Ionic Conductivities","ルオン フー ドック, 徐 陳超, ハレム ランディ, 館山 佳尚","ルオン フー ドック, 徐 陳超, ハレム ランディ, 館山 佳尚","IUMRS-ICAM & ICMAT 2023","IUMRS-ICAM & ICMAT 2023","2023-06-26","","eng","oral_presentation","","","","","","Herein, we simultaneously compare the electronic and ionic conductivities of two representative layered oxides LixTMO2 (where TM=Co, Ni and 0.6 We are working with DFT for the predictions. " "First-Principles DFT-based Computational Design of Novel Solid Electrolytes with Inverse Ruddlesden-Popper Tetragonal Structure for All-Solid-State Batteries","First-Principles DFT-based Computational Design of Novel Solid Electrolytes with Inverse Ruddlesden-Popper Tetragonal Structure for All-Solid-State Batteries","JALEM Randy, TATEYAMA Yoshitaka, TAKADA Kazunori, NAKAYAMA Masanobu","JALEM Randy, TATEYAMA Yoshitaka, TAKADA Kazunori, NAKAYAMA Masanobu","第62回電池討論会","第62回電池討論会","2021-11-30","","eng","oral_presentation","","","","","","A comprehensive DFT-based study was performed on >500 inverse Ruddlesden-Popper compounds for thermodynamic stability, ionic conductivity, surface (electro)chemical stability. (Chem. Mater. 2021, 33, 5859)","" "DFT approaches to electron and ion transfer in battery & DFT-based studies on battery issues","DFT approaches to electron and ion transfer in battery & DFT-based studies on battery issues","館山 佳尚","館山 佳尚","EU-Japan workshop on HPC-based material sciences","EU-Japan workshop on HPC-based material sciences","2021-11-08","","eng","oral_presentation","","","","","","DFT-MD/sampling has higher predictability, in principle. => We are working with DFT for the predictions.","" "Ion and Electron Transfer at Interfaces in Solid-state Batteries Via First-principles Calculations","Ion and Electron Transfer at Interfaces in Solid-state Batteries Via First-principles Calculations","館山 佳尚","館山 佳尚","International Battery Association 2021 (IBA 2021 Annual Meeting)","International Battery Association 2021 (IBA 2021 Annual Meeting)","2021-10-24","","eng","oral_presentation","","","","","","Interfacial resistance and degradation is one of the most essential issues for realization of solid-state battery (SSB). To understand the mechanisms on the atomic scale, we have recently developed an efficient sampling method of probable solid-solid interfaces [1]. Using the method with accurate density-functional-theory (DFT) calculations, we have explored a variety of solid-solid interfaces to acquire guiding principles to control the problems; sulfide, oxide and phosphate solid electrolytes (SEs) with Li metal anode or LiCoO2 cathode.","" "DFT study on interfaces in solid state battery via direct interface models","DFT study on interfaces in solid state battery via direct interface models","館山 佳尚","館山 佳尚","3rd WORLD CONFERENCE ON SOLID ELECTROLYTES FOR ADVANCED APPLICATIONS: GARNETS AND COMPETITORS","3rd WORLD CONFERENCE ON SOLID ELECTROLYTES FOR ADVANCED APPLICATIONS: GARNETS AND COMPETITORS","2021-10-25","","eng","oral_presentation","","","","","","1: Heterogeneous Interface CALYPSO method for interface structure sampling 2: DFT framework on standard (electro)chemical potential for interfacial ion transport 3: DFT study on stabilty & electronic states of Li/t-LLZO pristine & doped interfaces 4: DFT study on ion transport aroun c-LLZO grain boundaries","" "DFT-Based Computational Design Of Inverse Ruddlesden-Popper-Type Solid Electrolytes For All-Solid-State Lithium Ion Battery Application","DFT-Based Computational Design Of Inverse Ruddlesden-Popper-Type Solid Electrolytes For All-Solid-State Lithium Ion Battery Application","JALEM Randy, TATEYAMA Yoshitaka, TAKADA Kazunori, NAKAYAMA Masanobu","JALEM Randy, TATEYAMA Yoshitaka, TAKADA Kazunori, NAKAYAMA Masanobu","International Union of Materials Research Societies – International Conference in Asia 2021 (IUMRS-ICA 2021)","International Union of Materials Research Societies – International Conference in Asia 2021 (IUMRS-ICA 2021)","2021-10-03","","eng","oral_presentation","","","","","","Novel solid electrolyte design is one of the active research areas which is strongly linked to the practical application and large-scale commercialization of lithium ion all-solid-state batteries. In this work, by density functional theory (DFT) methods, we investigated the in-silico-generated material space of more than 500 inverse Ruddlesden-Popper-Type inorganic compounds with a general formula of Li4(X1-aX’a)(Z1-bZ’b)2, where X, X’ ϵ {O2-, S2-, Se2-, Te2-} and Z, Z’ ϵ {F-, Cl-, Br-, I-} in the 0 ≤ a, b ≤1 composition range. By DFT phase diagram approach, we determined about 167 thermodynamically (meta)stable novel compounds for potential use as lithium-based solid electrolytes, of which at least 20 novel compounds belong to the Li4O(Cl1-bBrb)2 series, O/I-bearing compositions, and O/S-bearing compositions. We further evaluated the screened compounds using DFT molecular dynamics in order to identify their characteristic transport Li+ ion transport mechanism. We will also present and discuss on computationally inexpensive, yet useful, material descriptors that we determined from this study for use in solid electrolyte design/search, in particular for phase stability and Li+ ion transport properties. ","" "Microscopic Electrochemistry of Ion Transport at Heterogeneous Solid-Solid Interface in Li-Ion Battery","Microscopic Electrochemistry of Ion Transport at Heterogeneous Solid-Solid Interface in Li-Ion Battery","館山 佳尚","館山 佳尚","IUMRS-ICA2021","IUMRS-ICA2021","2021-10-03","","eng","oral_presentation","","","","","","Interfacial charge-transfer processes in batteries govern their performance and stability, where both electronics and ionics play crucial roles. However, the electronic and atomistic understanding of such interface processes is still difficult in the conventional computational as well as experimental approaches. From theoretical side, we have addressed this issue based on the first principles density functional theory (DFT) calculations of the explicit solid-solid interfaces.","" "First-principles DFT study on the Na+ Superionic Conductivity in Cation-Doped Na3SbS4 Solid Electrolytes for All-Solid-State Batteries","First-principles DFT study on the Na+ Superionic Conductivity in Cation-Doped Na3SbS4 Solid Electrolytes for All-Solid-State Batteries","JALEM Randy, TATEYAMA Yoshitaka","JALEM Randy, TATEYAMA Yoshitaka","72nd Annual Meeting of the International Society of Electrochemistry","72nd Annual Meeting of the International Society of Electrochemistry","2021-08-29","","eng","oral_presentation","","","","",""," Na-ion batteries are especially sought for large-scale smart grids and other stationary applications, wherein the battery size factor is not the main concern during usage. Meanwhile, an all-solid-state Na+ ion battery (ASSB) design is highly desired in terms of safety and operation stability. However, to realize a high practical ASSB, there is a need to develop a solid electrolyte (SE) that can demonstrate high ionic conductivity in order to maximize energy density, such as when employing metal/alloy as the anode component. Recently, a sulfide-type Na+ ion conductor, cubic Na3SbS4 with W doping (Na2.88Sb0.88W0.12S4), was reported with unprecedented superionic conductivity at the level of 3.2 × 10-2 S cm-1, making the compound the champion SE in view of ionic conductivity for Na-ASSB application. In this work, we performed first-principles density functional theory molecular dynamics (DFT-MD) calculations for pristine, W-doped, and Mo-doped Na3SbS4 in order to examine the ionic conduction mechanism and the aliovalent cation dopant effects, in relation to the Boltzmann factor and the prefactor of ionic conductivity.2 We found that the diffusion process in Na3SbS4 is rather characterized by the concerted motion of Na+ ions. We determined that although Na vacancy concentration change induced by cation doping do indeed play a crucial role, the change in the number of vacancies alone cannot solely explain for the order of magnitude increase in conductivity. To clarify this issue, the pathway channels for Na+ ions and phonon density of states were analyzed in order to find correlations vs. jump frequencies and activation energy. Finally, we identified and suggested a computationally cheap conductivity descriptor which was derived from the Na+ ion pathway channel, for use as a general guiding principle for superionic conduction which may be applied not only for Na3SbS4 but also to other cations and SE systems. ","" "蓄電池がもたらすグリーン社会","蓄電池がもたらすグリーン社会","館山 佳尚","館山 佳尚","第155回 結晶工学分科会研究会 カーボンニュートラルに結晶工学が果たす役割","第155回 結晶工学分科会研究会 カーボンニュートラルに結晶工学が果たす役割","2021-06-23","","jpn","oral_presentation","","","","","","","本稿では,我々が確立してきた,構造秩序の低いヘテロな固固界面構造のサンプリングに関する高精度第一原理計算手法の紹介と,それを適用した全固体電池電極―電解質界面の第一原理計算研究について紹介した。その中で、界面におけるLi不安定サイトの存在と、""動的なLi空乏層の形成""および固体電解質の酸化の関連性、界面形成時とアニール後の挙動に関する計算アプローチについて議論した。さらに講演では本計算手法のガーネット型固体電解質、ニオブ酸化物緩衝層などへの応用8-11)についても紹介したいと思う。それとともに次世代蓄電池の有力候補である全固体電池の展望について議論したい。" "不均一系触媒反応の先進的第一原理計算研究","不均一系触媒反応の先進的第一原理計算研究","館山 佳尚","館山 佳尚","日本化学会 第101春季年会(2021)","日本化学会 第101春季年会(2021)","2021-03-19","","jpn","oral_presentation","","","","","","","本講演では、このような現象を考慮するための、従来型の第一原理触媒計算を越える先進的なアプローチについて概観する。特に第一原理計算を基本とした(1)電極触媒・光触媒を想定した酸化・還元反応に関するアプローチ、(2)反応速度論および化学工学計算を考慮した選択率等の評価について紹介する。" "大規模第一原理計算による全固体電池電解質界面のイオン・電子状態解明","大規模第一原理計算による全固体電池電解質界面のイオン・電子状態解明","館山 佳尚","館山 佳尚","「富岳」成果創出加速プログラム「富岳電池課題」第1回成果報告会","「富岳」成果創出加速プログラム「富岳電池課題」第1回成果報告会","2021-03-02","","jpn","oral_presentation","","","","","","","文部科学省「富岳」成果創出加速プログラム「次世代二次電池・燃料電池開発によるET革命に向けた計算・データ材料科学研究」(富岳電池課題)は2020年4月の発足から約1年が経過しました。本第1回公開シンポジウム(成果報告会)では、富岳電池課題の概要を課題責任者から、2020年度の成果を富岳電池課題実施者の中から4名の研究者がご報告いたします。" "DFT calculation study on Li metal / LLZO electrolyte interfaces: stability and ion transport","DFT calculation study on Li metal / LLZO electrolyte interfaces: stability and ion transport","館山 佳尚","館山 佳尚","Interface IONICS online symposium 2021 Spring","Interface IONICS online symposium 2021 Spring","2021-03-09","","eng","oral_presentation","","","","","","1: Introduction / Heterogeneous interface (HI) CALYPSO method for interface structure search, 2: DFT study on Li anode / Garnet Li7La3Zr2O12 SE interfaces, 3: DFT-MD study on Li7La3Zr2O12 Grain boundaries (GBs), 4: Discussion & Conclusion","" "Computational Design of Novel Solid Electrolytes with Inverse Ruddlesden-Popper Structures","Computational Design of Novel Solid Electrolytes with Inverse Ruddlesden-Popper Structures","JALEM Randy, TATEYAMA Yoshitaka, TAKADA Kazunori, NAKAYAMA Masanobu","JALEM Randy, TATEYAMA Yoshitaka, TAKADA Kazunori, NAKAYAMA Masanobu","CECAM Flagship Workshop: Materials Design for Energy Storage and Conversion: Theory and Experiment","CECAM Flagship Workshop: Materials Design for Energy Storage and Conversion: Theory and Experiment","2021-03-02","","eng","oral_presentation","","","","","","All-solid-state Li-ion batteries (Li-ASSBs) are now widely regarded as one of the most promising next-generation energy conversion and storage devices for the realization of low-carbon society. The solid electrolyte (SE) is one of the crucial components in Li-ASSBs which is required to satisfy multiple property criteria during battery work operation (e.g., high Li ionic conductivity, large electrochemical window, and good chemical stability). In this talk, we present our recent first-principles DFT calculation results on the material space of more than 500 in-silico-generated compounds with inverse Ruddlesden-Popper structure. We evaluated the compounds in terms of thermodynamic stability, chemical stability, Li ionic conductivity, and surface property and found a number of promising novel compounds for SE use. We also determined that a modified formulation of the Goldschmidt tolerance factor is a good descriptor for thermodynamic stability and electronic band gap energy of inverse Ruddlesden-Popper compounds.","" "DFT-based understanding of ion transfer at heterogeneous solid-solid interfaces in batteries","DFT-based understanding of ion transfer at heterogeneous solid-solid interfaces in batteries","館山 佳尚","館山 佳尚","CECAM Flagship Workshop: MATERIALS DESIGN FOR ENERGY STORAGE AND CONVERSION: THEORY AND EXPERIMENT ","CECAM Flagship Workshop: MATERIALS DESIGN FOR ENERGY STORAGE AND CONVERSION: THEORY AND EXPERIMENT ","2021-03-02","","eng","oral_presentation","","","","","","Interfacial charge-transfer processes in batteries govern their performance and stability, where both electronics and ionics play crucial roles. However, the electronic and atomistic understanding of such interface processes is still difficult in the conventional computational as well as experimental approaches.","" "炭酸リチウムSEI/グラファイト負極界面におけるLiイオン輸送の第一原理計算解析","炭酸リチウムSEI/グラファイト負極界面におけるLiイオン輸送の第一原理計算解析","館山 佳尚, 袖山 慶太郎","館山 佳尚, 袖山 慶太郎","第61回電池討論会","第61回電池討論会","2020-11-18","","jpn","oral_presentation","","","","","","","Understanding and control of Li-ion transport across the interface between anode and solid electrolyte interphase (SEI) or electrolyte is a key issue in battery electrochemistry. Herein, we investigated structural, electronic and free energy properties of Li-ion migration between Li-intercalated graphite anode LiCx and Li2CO3 SEI film, by using ab-initio molecular dynamics and free energy calculations. With the calculated free energy profiles for Li-ion and the electronic states of the interface systems, we deduced a general feature of Li-ion standard electrochemical potential profile and its variation in charging. The picture will give a useful insight into the Li-ion transport in battery." "Surface-Dependent Stability of the Interface between Garnet Li7La3Zr2O12 and the Li Metal in the All-Solid-State Battery from First-Principles Calculations","ガーネット型Li7La3Zr2O12/Li金属負極界面の安定性・酸化還元に関する第一原理計算研究","高 博, ハレム ランディ, 館山 佳尚","高 博, ハレム ランディ, 館山 佳尚","第61回電池討論会","第61回電池討論会","2020-11-18","","eng","oral_presentation","","","","","","The garnet-type Li7La3Zr2O12 (LLZO) solid electrolyte is of particular interest because of its good chemical stability and high ion conductivity, suitable for practical all-solidstate batteries (ASSBs). More promisingly, LLZO is regarded to be compatible with Li metal, enabling the utilization of the Li metal as an anode to achieve a battery with significantly high energy density. However, the electrochemical instability (e.g. interfacial Zr reduction) has been observed at the LLZO/Li interfaces. (1,2) These instability issues on the LLZO/Li interface lead to poor cycle stability and the increase of the interfacial resistance. Herein, we have revealed the possible origin of the instability by performing a comprehensive first-principles investigation with the interface structure search scheme in the CALYPSO method (3,4) combining with the density functional theory framework.","" "Mg(B(HFIP)4)2系電解質におけるMg金属析出反応機構の解明","Mg(B(HFIP)4)2系電解質におけるMg金属析出反応機構の解明","トウルソン フィロラ, 山本 健太郎, 万代 俊彦, 館山 佳尚, 中西 康次, 内山 智貴, 渡邊 稔樹, 金村 聖志, 内本 喜晴","トウルソン フィロラ, 山本 健太郎, 万代 俊彦, 館山 佳尚, 中西 康次, 内山 智貴, 渡邊 稔樹, 金村 聖志, 内本 喜晴","第61回電池討論会","第61回電池討論会","2020-11-18","","jpn","oral_presentation","","","","","","","Mg金属を負極に用いたマグネシウム二次電池は、理論体積容量密度・安全性・コストの点で優れており、次世代二次電池の候補の一つとして注目を集めている [1] 。近年、弱配位性アニオンから成るMg[B(HFIP)4]2 (HFIP= (CF3)2CHO) 電解質は、Mg(TFSA)2) 系電解質に比べてMg 析出溶解反応のクーロン効率が優れていることが報告されている [2] 。しかし、これらの電解質系においてなぜ Mg 析出溶解反応が可能であるかは明らかになっていない。そこで本研究ではこれらの電解質の Mg 析出過程における Mg2+の電子・局所構造をoperando軟 X 線吸収分光法(XAS)により分析し、Mg 金属析出反応機構の支配因子の解明を試みた。" "全固体電池開発に向けた計算・データ科学研究:富岳電池課題の取組","全固体電池開発に向けた計算・データ科学研究:富岳電池課題の取組","館山 佳尚","館山 佳尚","第61回電池討論会","第61回電池討論会","2020-11-18","","jpn","oral_presentation","","","","","","","文部科学省「富岳」成果創出加速プログラム採択課題「次世代二次電池・燃料電池開発によるET革命に向けた計算・データ材料科学研究」の概要と全固体電池に関する研究の進捗状況について紹介する。" "A Theoretical Study for Revealing the Mechanism of Sodiation in Hard Carbon for High Capacity Anode","A Theoretical Study for Revealing the Mechanism of Sodiation in Hard Carbon for High Capacity Anode","ユン ヨン, Azusa kamiyama, Kei Kubota, Sinichi Komaba, 館山 佳尚","ユン ヨン, Azusa kamiyama, Kei Kubota, Sinichi Komaba, 館山 佳尚","The 6th International Conference on Electronic Materials and Nanotechnology for Green Environment (ENGE 2020)","The 6th International Conference on Electronic Materials and Nanotechnology for Green Environment (ENGE 2020)","2020-11-01","","eng","oral_presentation","","","","","","Li-ion batteries have been widely used due to the lightweight, high energy density and rechargeability. However, their high price and limited quantities make it difficult to cope with the explosively increased usage for the energy storage. Recently, Na-ion batteries have attracted as an alternative of LIBs. For emerging Na ion batteries, the development of high-performance anodes is crucial. Hard carbon is one of the most promising candidates with excellent potential. Nonetheless, the sodiation mechanism is still unclear and a debatable topic. Here, we introduced a plausible scenario for the sodiation in the hard carbon using the density functional theory calculation. Based on the “house of cards” model, we evaluated the formation energy of several Na-C configurations considering the active sites in hard carbon except for the electrolyte contributed sites related to the irreversible capacity. As a result, we clarified that the origin of plateau capacity is both intercalation in the graphitic domains and adsorption in the close-pores. Whereas, the defect and edge sites contribute to the slope capacity. Furthermore, we identified that close-pore is the most important site to exceed the current capacity of hard carbon about 300 mAh/g, and proposed a geometry of hard carbon for high capacity. This work was performed using supercomputer “Fugaku” in Japan.","" "DFT Sampling Studies on Interface Ionics at Heterogeneous Solid-Solid Interfaces in Batteries","DFT Sampling Studies on Interface Ionics at Heterogeneous Solid-Solid Interfaces in Batteries","館山 佳尚","館山 佳尚","The 6th International Conference on Electronic Materials and Nanotechnology for Green Environment (ENGE2020)","The 6th International Conference on Electronic Materials and Nanotechnology for Green Environment (ENGE2020)","2020-11-01","","eng","oral_presentation","","","","","","Interface processes in energy devices such as batteries and solar cells largely govern their performance and stability, where both electronics and ionics play crucial roles. To understand such interfacial processes, however, typical static geometry optimization or even molecular dynamics (MD) based on DFT framework does not work well due to the inherent heterogeneous and multiscale characters. On the other hand, empirical methods such as classical MD are still insufficient because their parameters are usually fitted to bulk properties, not interface. In this situation, effective sampling technique within with DFT framework is indispensable. In this talk, I will introduce DFT sampling approaches recently implemented in our group for disorderd heterogeneous solid-solid interfaces and our researches on the inonics at oxide cathode / sulfide electrolyte interfaces in all-solid-state batteries [1-4]. The sampling breakthrough was achieved by the CALYPSO technique [5,6], which allows us to explore a variety of interfacial disordered structures. The approach is compatible to massive parallel calculations with high performance computing resources like “Fugaku”. The sampled interfacial structures enable to examine the chemical potential and potential energy surface of mobile ions around the solid-solid interfaces, which gives a perspective about the interfacial space-charge and electric double layers as well as their relations with the interface ionics.","" "次世代二次電池・燃料電池開発によるET革命に向けた計算・データ材料科学研究","次世代二次電池・燃料電池開発によるET革命に向けた計算・データ材料科学研究","館山 佳尚","館山 佳尚","第10回材料系ワークショップ ~「富岳」時代の物質科学シミュレーションの新展開~","第10回材料系ワークショップ ~「富岳」時代の物質科学シミュレーションの新展開~","2020-10-16","","jpn","oral_presentation","","","","","","","文部科学省「富岳」成果創出加速プログラム採択課題「次世代二次電池・燃料電池開発によるET革命に向けた計算・データ材料科学研究」の概要と研究進捗状況について紹介する。" "Critical Issues of Fluorinated Alkoxyborate-based Electrolytes in Magnesium Battery Applications","Critical Issues of Fluorinated Alkoxyborate-based Electrolytes in Magnesium Battery Applications","万代 俊彦, 石川 敦之, 館山 佳尚","万代 俊彦, 石川 敦之, 館山 佳尚","PRiME2020","PRiME2020","2020-10-04","","eng","oral_presentation","","","","","","Development of non-corrosive but highly efficient electrolytes has been long-standing challenges in magnesium rechargeable battery (MRB) research fields. The surface passivation film formed upon undesired reactions of magnesium metal with conventional electrolytes indeed inhibits efficient interfacial electrochemical reactions. In recent years, the new class of electrolyte materials has been reported, and these electrolytes especially incorporating the weakly coordinated anions (WCAs) have overcome some serious problems associated with conventional electrolytes.1–3 Among the reported WCA-based electrolytes, certain fluorinated alkoxyborate-based electrolytes, e.g. Mg[B(HFIP)4]2/glyme (HFIP = hexafluoroisopropoxy-group), are regarded as promising candidates for practical MRB materialization owing to the excellent electrochemical activity and good synthetic accessibility. We herein report several critical issues associated with the use of Mg[B(HFIP)4]2/glyme electrolytes in MRBs. The electrolyte containing Mg[B(HFIP)4]2 prepared from Mg(BH4)2 requires several ten-cycles of pre-activation process. The reductive decomposition of glymes (not [B(HFIP)4]−) in the electrolyte solutions takes place upon just contacting the electrolytes with magnesium metal. Non dendritic short-circuit should also be solved for practical application.","" "Theoretical Analysis of Microscopic Interface Ionics at Heterogeneous Solid-Solid Interfaces in Batteries","Theoretical Analysis of Microscopic Interface Ionics at Heterogeneous Solid-Solid Interfaces in Batteries","館山 佳尚","館山 佳尚","PRiME2020","PRiME2020","2020-10-04","","eng","oral_presentation","","","","","","All-solid-state battery (ASSB) has attracted considerable attention for decades, and the developments of many new materials appropriate for ASSB have been made. In contrast, less is known about the interfacial processes, especially at the solid electrolyte (SE)-electrode interfaces. The microscopic origins of interfacial resistance and degradation are still crucial issues for the efficient ASSBs, which are closely related to the interface chemistry and electrochemistry on the ionic and electronic scales. Therefore, understanding of the microscopic interface ionics and electronics is indispensable for the cutting-edge ASSB development. We have addressed establishing a universal calculation framework based on density functional theory (DFT) for heterogeneous solid-solid interfaces. Typical DFT geometry optimization or molecular dynamics does not work well for the atomistic structure search due to the coexistence of collective and local geometry relaxations inherent to the solid-solid interfaces. The methods with empirical force field are also insufficient because their parameters are usually fitted to bulk properties, not interfacial ones.","" "蓄電池材料・現象の先端的第一原理計算研究","蓄電池材料・現象の先端的第一原理計算研究","館山 佳尚","館山 佳尚","電気化学界面シミュレーションコンソーシアム 2020年度第1回研究会","電気化学界面シミュレーションコンソーシアム 2020年度第1回研究会","2020-10-02","","jpn","oral_presentation","","","","","","","文部科学省「富岳」成果創出加速プログラム採択課題「次世代二次電池・燃料電池開発によるET革命に向けた計算・データ材料科学研究」の概要と、NIMS館山研究室で行っている二次電池固固界面に関する第一原理計算研究について紹介する。" "A03 理論・計算・データ科学班研究報告","A03 理論・計算・データ科学班研究報告","館山 佳尚","館山 佳尚","「蓄電固体界面科学」第2回公開シンポジウム","「蓄電固体界面科学」第2回公開シンポジウム","2020-09-28","","jpn","oral_presentation","","","","","","","2019年7月に発足した科研費・新学術領域研究「蓄電固体界面科学」も約1年か経過しました。この1年間のA03班研究成果について報告する。" "ヘテロ固固界面構造探索手法の開発と全固体電池界面への適用","ヘテロ固固界面構造探索手法の開発と全固体電池界面への適用","ハレム ランディ, 高 博, 館山 佳尚","ハレム ランディ, 高 博, 館山 佳尚","日本セラミックス協会 第33回秋季シンポジウム","日本セラミックス協会 第33回秋季シンポジウム","2020-09-02","","jpn","oral_presentation","","","","","",""," 現在、全固体電池などの蓄電固体デバイスの開発が急速に進められています。しかしこのような固体デバイスには内部に多数の固固体界面が存在し、その低いイオン電導性や不安定性が要求性能達成のボトルネックとなっています。その改善指針を得るために、これらの固固界面をミクロレベルで理解することが必要不可欠ですが、現在の実験及び計算技術をもってしてもデバイス動作条件での固固界面の電子・イオン状態を把握することは大変困難でした。  本研究では、異なる材料間のヘテロ固固界面における原子・イオンの格子不整合、集団緩和、局所緩和に関するあらゆる最適化と、高効率構造予測計算手法CALYPSO法の界面構造探索への適用、電子状態を高精度に取り扱える密度汎関数理論(DFT)計算を全て組み合わせることで、ヘテロ固固界面んお量子論・統計論に基づく理解を可能にする高精度シミュレーション手法の開発に成功しました。一般的な固固界面に対する系統的な第一原理構造探索手法としては世界初のものとなっています。  さらに、硫化物系全固体電池の酸化物正極(LiCoO2)ー硫化物電解質(Li3PS4)界面に適用し、界面のイオン伝導抵抗のミクロな起源としての、電解質界面の電子移動、Liイオンの動的な欠乏、界面電気化学反応らの関係について、実験結果を包括的に説明できる理論の実証に成功しました。さらにLi金属負極ー酸化物固体電解質Li7La3Zr2O12界面に対しても適用し、安定な界面群の抽出とそれらを元にした界面酸化還元反応の微視的機構解明も行いました。" "不均一系触媒によるレドックス反応の理論計算解析","不均一系触媒によるレドックス反応の理論計算解析","館山 佳尚","館山 佳尚","日本化学会第100春季年会","日本化学会第100春季年会","2020-03-22","","jpn","oral_presentation","","","","","","","不均一系触媒反応は、酸化物や金属等の固体表面に気相・液相内の反応物が吸着することで、反応の活性化エネルギーが低下し促進される触媒反応である。この反応を理論計算により解析する場合、反応物や生成物の表面吸着エネルギーとそれらの間の反応エネルギープロファイルを密度汎関数理論(DFT)を基にした第一原理計算で求め、活性化エネルギーの低下を示すという方法がよく用いられる。これを様々な表面で行うと吸着エネルギーを記述子とするvolcano plotが得られ、適度な反応物吸着と生成物脱着を持つ表面が活性が高いという傾向が得られる。" "First-principles study on electrode-contact chemical stability and Na ion dynamics of Na3SbS4 solid electrolyte for all-solid-state Na ion batteries","First-principles study on electrode-contact chemical stability and Na ion dynamics of Na3SbS4 solid electrolyte for all-solid-state Na ion batteries","JALEM Randy, TATEYAMA Yoshitaka","JALEM Randy, TATEYAMA Yoshitaka","2020 APS March Meeting","2020 APS March Meeting","2020-03-02","","eng","oral_presentation","","","","","","To enhance safety, the replacement of the combustible organic-/liquid-based electrolyte in sodium ion batteries with a ceramic-based solid electrolyte has been sought. In this talk, we present our results on thermodynamic and ion dynamics analyses of Na3SbS4 solid electrolyte using first-principles calculations. Based from the calculated chemical potential diagram when Na3SbS4 is in contact with possible layered cathode compounds Na[TM]O2 (where TM = {V, Cr, Mn, Fe, Co, Ni}), sulfur has the driving force to migrate across the electrolyte-cathode interface which may partly explain the experimentally observed formation of interface reaction layer in such all-solid state battery interfaces. From space-time correlation analysis of molecular dynamics trajectory, we determined a concerted migration behavior for Na ions which can explain for the material's superionic conductivity behavior (>10-3 S/cm). The effects of halide doping on the conductivity behavior of Na3SbS4 will also be discussed.","" "「京」コンピュータを駆使した第一原理MD法による電解液開発支援","「京」コンピュータを駆使した第一原理MD法による電解液開発支援","館山 佳尚","館山 佳尚","第4回元素戦略シンポジウム","第4回元素戦略シンポジウム","2020-02-03","","jpn","oral_presentation","","","","","",""," リチウムイオン電池(LIB)などの二次電池の大型化、安全性強化はエネルギー・環境問題のソリューションやSociety 5.0への貢献のみならず、社会構造を劇的に変えうる重要課題です。その核心は安全な電解液・電解質の開発、および電極―電解質界面の制御と言って良いでしょう。しかし、二次電池内の電子・イオンの動きは複雑なため、実験的に全貌を明らかにすることは未だ困難であり、試行錯誤的な研究開発がまだ大半です。  このような状況を打破すべく、「京」コンピュータなどの大型スパコンを駆使した計算(+データ)科学研究に、筆者らは取り組んできました。それらの事例について紹介します。" "「京」を用いた蓄電池の計算科学研究","「京」を用いた蓄電池の計算科学研究","館山 佳尚","館山 佳尚","高分子同友会勉強会「新材料の創製(反応、合成、バイオ、触媒、解析、機能等)について勉強する会」","高分子同友会勉強会「新材料の創製(反応、合成、バイオ、触媒、解析、機能等)について勉強する会」","2020-01-28","","jpn","oral_presentation","","","","","","","計算ハードウェアおよびソフトウェアの進歩により、実験でも同定が難しい蓄電池内部の複雑な現象に対して、精度の高い計算解析が可能となってきた。本講演では、今はなき「京」コンピュータ等を用いて私が取り組んだ蓄電池電解液、電解質、界面の計算研究について紹介したい。" "Computational screening of novel solid electrolyte candidates for all-solid-state battery by high-throughput DFT and data science techniques","Computational screening of novel solid electrolyte candidates for all-solid-state battery by high-throughput DFT and data science techniques","JALEM Randy, TATEYAMA Yoshitaka, TAKEUCHI Ichiro, NAKAYAMA Masanobu","JALEM Randy, TATEYAMA Yoshitaka, TAKEUCHI Ichiro, NAKAYAMA Masanobu","Materials Research Meeting 2019","Materials Research Meeting 2019","2019-12-10","","eng","oral_presentation","","","","","","In this talk, recent efforts from our group for developing efficient computational methodologies for finding novel fast ionic conductors for potential use in all-solid-state batteries, including their challenges that need addressing, will be presented. One major issue that we focused to address is the computationally prohibitive cost of calculating transition-state-related properties (e.g., ionic conductivity, ion migration energy barrier) at the DFT-level accuracy, these properties are crucial for knowing whether a material is useful for battery application. We formulated a workflow wherein the DFT method that calculates the computation-intensive property is embedded into a Bayesian optimization framework. We demonstrate the efficiency of the method by screening on relatively unexplored material spaces of inorganic compounds, with using schemes of single-property search criterion as well as multiple-property search criteria.","" "Multiple Adsorption Modes and Decomposition Pathways of Carbonate Electrolyte Molecules at LiNi0.5Mn1.5O4 Cathode Interfaces: Ab Initio Study","Multiple Adsorption Modes and Decomposition Pathways of Carbonate Electrolyte Molecules at LiNi0.5Mn1.5O4 Cathode Interfaces: Ab Initio Study","館山 佳尚, シュクリ ガネス, Keisuke Ushirogata, Yukihiro Okuno, Yukihiro Okuno","館山 佳尚, シュクリ ガネス, Keisuke Ushirogata, Yukihiro Okuno, Yukihiro Okuno","Materials Research Meeting 2019 (MRM2019)","Materials Research Meeting 2019 (MRM2019)","2019-12-10","","eng","oral_presentation","","","","","","Recently, electrolyte-cathode interfaces have attracted much attention for cathode degradation, oxidative decomposition of electrolyte and cahode electrolyte interphase (CEI) formation. However, the studies on the cathode interfaces are still lacking, compared to the more famous anode interfaces and SEI fims. Themodynamically, the oxidation potential of typical liquid electrolyte is usualy in the stable region against the cathode oxidation. On the other hand, CO2 gas evolution from the cathode side was observed recently. In this work, we investigated properties of cathode / electrolyte interfaces, in particular (1) the eletrolyte adsorption manner under equilibrium and (2) the electrolyte decomposition processes, by using density functional theory (DFT) calculations. Here we focused on LiNi0.5Mn1.5O4 (LNMO) (100) / ethylene carbonate (EC) interfaces.","" "Microscope mechanism of Li-ion transport at Interfaces between LiCoO2 Cathode and Sulfide Electrolyte in All-Solid-State Battery via DFT-CALYPSO Method","Microscope mechanism of Li-ion transport at Interfaces between LiCoO2 Cathode and Sulfide Electrolyte in All-Solid-State Battery via DFT-CALYPSO Method","高 博, ハレム ランディ, Yanming Ma, 館山 佳尚","高 博, ハレム ランディ, Yanming Ma, 館山 佳尚","Materials Research Meeting 2019","Materials Research Meeting 2019","2019-12-10","","eng","oral_presentation","","","","","","All-Solid-state batteries (ASSBs) is of great interest because of its high safety and high energy density in comparison to traditional liquid electrolytes based batteries. However, there is a crucial issue about the interface resistance between the cathode and electrolyte in many ASSBs, which hinders the performance of batteries. To understand the microscopic mechanism of the interface resistance, we have been working on the DFT calculation analysis of the cathode – solid electrolyte interfaces with a systematic structure search[1][2]. However, the explorations were still insufficient. Note that solid-solid interfaces seem more difficult than solid-liquid ones from a viewpoint of search for metastable structures. In this study, we systemically investigate the interface configurations between LiCoO2 cathode and Li3PS4 sulfide solid electrolyte using CALYPSO structure prediction approach[3][4]. It is found that energetically stable and metastable structures. Several efficient techniques have been applied in our method, including an automatic toolkit for searching matched superlattice, a structure generation method including the lattice displacement, and PSO algorithm. For the obtained energetically favorable structures, we calculated the electronic states and Li vacancy formation energies. We found that the interfacial layer is formed accompanied by the cation mixing (Co ↔ P exchange) and anion mixing (O ↔ S exchange). We then revealed that there are interfacial Li sites where preferential Li depletion can occur upon charging, even in very disordered interfaces. This suggests that the space-charge layer mechanism plays a major role for the interfacial resistance. Besides, the present study demonstrated how to explore the structures of solid-solid interfaces at the atomic scale.","" "Effects of Magnesium-Organo-Haloaluminate complex in Magnesium Ion Battery Electrolytes: A Car-Parrinello Molecular Dynamics Study","Effects of Magnesium-Organo-Haloaluminate complex in Magnesium Ion Battery Electrolytes: A Car-Parrinello Molecular Dynamics Study","チョーダリー アシュ, 袖山 慶太郎, 館山 佳尚","チョーダリー アシュ, 袖山 慶太郎, 館山 佳尚","Materials Research Meeting 2019 (MRM2019)","Materials Research Meeting 2019 (MRM2019)","2019-12-10","","eng","oral_presentation","","","","","","Mg-ion batteries (MIBs) have attracted much attention for next-generation batteries [1-3]. However, understanding of the microscopic processes such as deposition/dissolution, passivation layer effect, ion transport in electrodes, and guideline for the optimal electrolytes and electrodes have not been established yet. Recently, studies combining experiments and computations have appeared and suggested several interesting aspects of MIBs [2,3]. In this study, we addressed understanding of the deposition / dissolution behaviour in MIBs, adopting a representative electrolyte of Grignard reagent (RMgCl) in tetrahydrofuran (THF), through the first-principles Car-Parrinello molecular dynamics simulations together with recent experimental data. In particular, we focus on the vibration spectra and the electronic states of the solvation shell in the possible intermediate states of the deposition / dissolution. We also analyse the effect of the AlCl3 additive, as this has a certain impact for the deposition / dissolution behaviour. Electro-active species MgCl+ and its solvation shell has been studied in detail to understand the mechanism of charge transfer [4].","" "Lithium Diffusion Mechanism in Highly Concentrated Electrolytes via First-Principles Molecular Dynamics Sampling","Lithium Diffusion Mechanism in Highly Concentrated Electrolytes via First-Principles Molecular Dynamics Sampling","ソン ヤン, 袖山 慶太郎, Yuki Yamada, 館山 佳尚, Atsuo Yamada","ソン ヤン, 袖山 慶太郎, Yuki Yamada, 館山 佳尚, Atsuo Yamada","Materials Research Meeting 2019 (MRM2019)","Materials Research Meeting 2019 (MRM2019)","2019-12-10","","eng","oral_presentation","","","","",""," Improvement of battery safety, keeping the performace, is an important issue in the battery research community. Thermal runaway of “organic electrolyte” induced by electrochemical reactions is a major trouble. Intefacial films play roles of preventing the electrolyte decomposition. However, development of stable electrolyte is also indispensible. Our collaboration has proposed use of highly salt-concentrated electrolytes. Highly concentrated (HC) 4.2M LiTFSA/AN electrolyte shows strong and stable stability agaist reduction. In typical low concentration (LC) electrolyte such as 1.0M LiTFSA/AN, the reductive decomposition of electrolyte occurs, causing change of the colour.","" "第一原理酸化還元反応シミュレーション","第一原理酸化還元反応シミュレーション","館山 佳尚","館山 佳尚","第33回分子シミュレーション討論会","第33回分子シミュレーション討論会","2019-12-09","","jpn","oral_presentation","","","","","","","酸化還元反応(電子移動反応)は物性科学、分子科学、生体物理など多様な分野において重要素過程として現れる。例えば、二次電池、電極触媒、均一系触媒、光合成、呼吸などはすべて酸化還元反応が中心的な役割を果たす。酸化還元反応・電子移動反応の理論はすでに、Marcus、Warshelらによって確立されてきたが、それを”定量的に”扱える理論計算フレームワークとして構築することは、様々な具体的課題を計算シミュレーションで解決するうえで重要である。このような動機付けのもと、筆者は酸化還元反応シミュレーション手法の開発に取り組んできた。本講演では(最近の二次電池の応用計算も紹介しつつ)それら理論計算について紹介する。" "エネルギー物質科学と界面イオニクス・エレクトロニクス","エネルギー物質科学と界面イオニクス・エレクトロニクス","館山 佳尚","館山 佳尚","第58回玉城嘉十郎教授記念公開学術講演会","第58回玉城嘉十郎教授記念公開学術講演会","2019-12-09","","jpn","oral_presentation","","","","","","","2つの相が接触する界面(固液界面、固固界面、固気界面=表面など)では、イオン・電子移動により各相固有のイオン・電子状態とは異なる状態が現れ、それがエネルギー貯蔵・変換に関して重要な役割を果たします。実際、電池や触媒のほとんどがこの界面の特徴を利用しています。半導体物理や電気化学分野において界面理論はすでに確立しているように見えますが、界面におけるイオンと電子の相関したダイナミクスを真に理解するには、既存分野を融合した新しいフレームワークが必要となります。この目標に向けて、私は密度汎関数理論を基にした電子・イオン・分子・凝縮体の第一原理“サンプリング”計算を用いて、界面におけるイオン・電子の平衡・定常状態の解明を進めてきました。本講演では、界面イオニクス・エレクトロニクスについて俯瞰したのち、蓄電池・触媒などのエネルギー物質科学に関する我々の理論計算研究の成果について紹介します。" "Structure Search and Property Analysis of Interfaces between Cathode and Solid Electrolyte in All-Solid-State Battery via DFT-CALYPSO Method","Structure Search and Property Analysis of Interfaces between Cathode and Solid Electrolyte in All-Solid-State Battery via DFT-CALYPSO Method","高 博, ハレム ランディ, Yanming Ma, 館山 佳尚","高 博, ハレム ランディ, Yanming Ma, 館山 佳尚","The 10th Asian Conference on Electrochemical Power Sources 2019 (ACEPS-10)","The 10th Asian Conference on Electrochemical Power Sources 2019 (ACEPS-10)","2019-11-24","","eng","oral_presentation","","","","","","All-Solid-state batteries (ASSBs) is of great interest because of its high safety and high energy density in comparison to traditional liquid electrolytes based batteries. However, there is a crucial issue about the interface resistance between the cathode and electrolyte in many ASSBs, which hinders the performance of batteries. To understand the microscopic mechanism of the interface resistance, we systemically investigate the interface configurations between LiCoO2 cathode and Li3PS4 sulfide solid electrolyte using CALYPSO structure prediction approach. Several efficient techniques have been applied in our method, including an automatic toolkit for searching matched superlattice, a structure generation method including the lattice displacement, and PSO algorithm. For the obtained energetically favorable structures, we calculated the electronic states and Li vacancy formation energies. We found that the interfacial layer is formed accompanied by the cation mixing (Co ↔ P exchange) and anion mixing (O ↔ S exchange). We then revealed that there are interfacial Li sites where preferential Li depletion can occur upon charging, even in very disordered interfaces. Besides, the present study demonstrated how to explore the structures of solid-solid interfaces at the atomic scale.","" "Insights on the electrode-contact stability and ion conduction mechanism in Na3SbS4 solid electrolyte by DFT-based calculations","Insights on the electrode-contact stability and ion conduction mechanism in Na3SbS4 solid electrolyte by DFT-based calculations","JALEM Randy, TATEYAMA Yoshitaka","JALEM Randy, TATEYAMA Yoshitaka","The 10th Asian conference on Electrochemical Power Source 2019(ACEPS10) https://aceps10.org/index.php","The 10th Asian conference on Electrochemical Power Source 2019(ACEPS10) https://aceps10.org/index.php","2019-11-24","","eng","oral_presentation","","","","","","Many research works now focus on alternative technologies beside Li-ion rechargeable batteries, one being based on the highly abundant Na element. This is due to cost and accessibility issues associated with Li and the ever increasing desire of society to tap more on clean/renewable energy sources that have less carbon footprint. All-solid-state Na-ion battery (ASS-NIB) is now widely regarded as one of the promising storage systems for applications such as smart grid system and stationary back-up power. For a practical ASS-NIB, a high-performance solid electrolyte is required, specifically in terms of (electro)chemical stability and Na ionic conductivity. In this presentation, we used density functional theory (DFT) calculations in order to investigate the electrode-contact stability and Na-ion conduction property of a recently reported solid electrolyte compound with nominal composition Na3SbS4.[1] Analysis of chemical potential range of stability for various relevant element species have shown that when in contact with possible cathodes with layered compound structure (Na[TM]O2, where TM = {V, Cr, Mn, Fe, Co, Ni}), some of the species have the tendency to move across the cathode-electrolyte interface, possibly driving the atomic rearrangement, disordering and/or decomposition around the interface region. Based from kinetic modelling at the anode-electrolyte contact, stresses at typical electrodeposition surface roughness would enable Na dendrite initiation at the surface of the metal anode. On the other hand, results from defect chemistry and nudged elastic band calculations suggest a 3D pathway comprised with vacancy and interstitial sites. Na ion migration energies were determined to be enormously low, less than 0.10 eV. The effects of halide doping towards ionic conductivity were also analyzed in terms of Boltzmann factor and lattice softness. ","" "Computational and Theoretical Electrochemistry of Li-ion States around Electrode / Solid Electrolyte Interfaces","Computational and Theoretical Electrochemistry of Li-ion States around Electrode / Solid Electrolyte Interfaces","館山 佳尚","館山 佳尚","10th Asian Conference on Electrochemical Power Sources 2019 (ACEPS10)","10th Asian Conference on Electrochemical Power Sources 2019 (ACEPS10)","2019-11-24","","eng","oral_presentation","","","","","","All-solid-state batteries (ASSBs) have been regarded as promising next-generation Li-ion batteries (LIBs), and desirable solid electrolytes (SEs) with higher Li-ion conductivities have been found. However, the high interfacial resistance of Li-ion transport at the electrode – SE interface remains a crucial bottleneck. Although interposing a buffer layer onto the interface has been used to remedy this problem in practice [1], the fundamental mechanism is still under significant debate. We have been exploring the atomistic understanding of this interfacial resistance mechanism with DFT-based calculations [2,3]. We first devised some systematic ways for the solid-solid interfaces and discussed possible origins such as the space-charge layer and the reaction layer. Recently, we incorporated the CALYPSO structure prediction technique with our method for the interface structure search, including mismatch treatment and lateral shift etc. [4]. In this way, we have found several microscopic electrochemistry of the interfacial Li-ion states [5]. As a representative model, we investigated the system with LiCoO2 (LCO), β-Li3PS4 (LPS), and LiNbO3 (LNO) acting as a cathode, a sulfide electrolyte, and a buffer layer, respectively. For the LCO/LPS interfaces, we sampled over 20000 configurations and found several stable disordered structures involving mixing cations and anions, leading to the formation of a reaction layer. On the other hand, Li-ion sites that can be preferentially depleted upon charging always exist around the cathode-SE interfaces irrespective of the interfacial order/disorder (See Li Chemical potential in Figure). Therefore, we conclude that the dynamic Li-ion depletion is likely to be a major cause that prevents successive Li-ion transport, leading to resistance. Through investigating the buffer layer effects and the interfacial electronic states, we also deduced a probable origin for the interfacial Li depletion and a mean to suppress this problematic behavior. ","" "Electrochemical properties ofMg battery electrolytes with weakly coordinated anions","弱配位性アニオンを有するMg系電解液の電気化学特性","袖山 慶太郎, 館山 佳尚, 万代 俊彦, 金村 聖志","袖山 慶太郎, 館山 佳尚, 万代 俊彦, 金村 聖志","第60回電池討論会","第60回電池討論会","2019-11-13","","jpn","oral_presentation","","","","","","","Mg電池用電解液として近年特に有望視されている、弱配位性アニオンを対イオンとした一連のMg塩(Mg[Z(ORF)]2)を合成し、その電気化学特性を評価した。分岐のあるアルコキシ基を導入した場合に優れた特性を発揮し、Mg析出溶解の電流密度はCl含有電解液に匹敵した。電解液中でMg2+と[Z(ORF)]-が高度に解離していることが、その要因の一つと考えられる。" "DFT-based study on the electrode-contact stability and ion transport of Na3SbS4 solid electrolyte for all-solid-state batteries","DFT-based study on the electrode-contact stability and ion transport of Na3SbS4 solid electrolyte for all-solid-state batteries","TATEYAMA Yoshitaka, JALEM Randy","TATEYAMA Yoshitaka, JALEM Randy","The 60th Battery Symposium in Japan","The 60th Battery Symposium in Japan","2019-11-13","","eng","oral_presentation","","","","","","All-solid-state Na-ion battery (ASS-NIB) is now becoming strongly sought as promising storage system where volumetric capacity and form factor are not as crucial such as in smart grid and stationary application. To realize this system, a highly stable and highly ionic-conductive solid electrolyte is requested. In this work, the electrode-contact stability and Na-ion transport of a recently reported solid electrolyte Na3SbS4 was investigated by using density functional theory (DFT) calculations.","" "Force Field Parameterization using Genetic Algorithm for Lithium-Ion Battery Applications","Force Field Parameterization using Genetic Algorithm for Lithium-Ion Battery Applications","ガオ シーチャン, 館山 佳尚, 赤木和人","ガオ シーチャン, 館山 佳尚, 赤木和人","22nd Asian Workshop on First-Principles Electronic Structure Calculations (ASIAN-22)","22nd Asian Workshop on First-Principles Electronic Structure Calculations (ASIAN-22)","2019-10-28","","eng","oral_presentation","","","","","","Commercially viable and environmental friendly electrochemical storage systems are playing crucial roles in solving social problems. Among them, further improvement of lithium-ion batteries (LIB) are regarded as promising and realistic solution. The performance of LIB depends on various factors, but ion transport properties are one of the most important items. However, the mechanism of lithium ion transport in electrolytes remains elusive so far. Many force fields such as AMOEBA and APPLE&P have the potential to be applied to large scale simulation for LIB applications, but the problem is in lack of reliable parameter sets. Force field parameterization is a challenging and time-consuming process. In order to elucidate the mechanism of lithium transport, we have developed a genetic algorithm based force field for the lithium-ion battery applications.","" "Structure Search and Property Analysis of Interfaces between Cathode and Solid Electrolyte in All-Solid-State Battery via DFT-CALYPSO Method","Structure Search and Property Analysis of Interfaces between Cathode and Solid Electrolyte in All-Solid-State Battery via DFT-CALYPSO Method","高 博, ハレム ランディ, Yanming Ma, 館山 佳尚","高 博, ハレム ランディ, Yanming Ma, 館山 佳尚","The 22nd Asian Workshop on First-Principles Electronic Structure Calculations (ASIAN-22)","The 22nd Asian Workshop on First-Principles Electronic Structure Calculations (ASIAN-22)","2019-10-28","","eng","oral_presentation","","","","","","All-Solid-state batteries (ASSBs) is of great interest because of its high safety and high energy density in comparison to traditional liquid electrolytes based batteries. However, there is a crucial issue about the interface resistance between the cathode and electrolyte in many ASSBs, which hinders the performance of batteries. To understand the microscopic mechanism of the interface resistance, we systemically investigate the interface configurations between LiCoO2 cathode and Li3PS4 sulfide solid electrolyte using CALYPSO structure prediction approach[1]. Several efficient techniques have been applied in our method, including an automatic toolkit for searching matched superlattice, a structure generation method including the lattice displacement, and PSO algorithm. For the obtained energetically favorable structures, we calculated the electronic states and Li vacancy formation energies. We found that the interfacial layer is formed accompanied by the cation mixing (Co ↔ P exchange) and anion mixing (O ↔ S exchange). We then revealed that there are interfacial Li sites where preferential Li depletion can occur upon charging, even in very disordered interfaces. Besides, the present study demonstrated how to explore the structures of solid-solid interfaces at the atomic scale. ","" "The Oxidative Coupling of Methane Catalyzed by MgO; A First-Principle Based Microkinetics and Ab-initio Molecular Dynamics Study","The Oxidative Coupling of Methane Catalyzed by MgO; A First-Principle Based Microkinetics and Ab-initio Molecular Dynamics Study","石川 敦之, 館山 佳尚","石川 敦之, 館山 佳尚","22nd Asian Workshop on First-Principles Electronic Structure Calculations (ASIAN-22)","22nd Asian Workshop on First-Principles Electronic Structure Calculations (ASIAN-22)","2019-10-28","","eng","oral_presentation","","","","","","The oxidative coupling of methane (OCM) has long been studied becuase it is an effective approach to make higher hydrocarbons from natural gas. The reaction mechanism is complicated because it involves both gas-phase and surface-mediated reactions. For the full understanding on the reaction mechanism, theoretical study, especially from atomic or molecular level is helpful. At the same time, macroscopic scale simulation is also important from practical aspect becuase estimation of activity such as CH4 conversion and selectivity of target C2 compounds is needed to discover new catalyst systems. To this aim, we carried out density functional theory (DFT) combined with microkinetics and chemical reactor modeling, as this approach enables the activity and selectivity prediction from atomic or molecular level simulations.","" "DFT Sampling Studies on Interface Ionics at Disordered Heterogeneous Solid-Solid Interfaces","DFT Sampling Studies on Interface Ionics at Disordered Heterogeneous Solid-Solid Interfaces","館山 佳尚","館山 佳尚","2nd Asian Workshop on First-Principles Electronic structure Calculations (ASIAN-22)","2nd Asian Workshop on First-Principles Electronic structure Calculations (ASIAN-22)","2019-10-28","","eng","oral_presentation","","","","","","Interface (and surface) processes in energy and environmental devices such as batteries and catalysts largely govern their performance and stability, where both electronics and ionics play crucial roles. To understand such interfacial processes, however, typical static geometry optimization or even molecular dynamics (MD) based on DFT framework does not work well often due to the inherent heterogeneous and multiscale characters. On the other hand, parameter-based methods such as classical MD are still insufficient from a viewpoint of predictability because their parameters are usually fitted to bulk properties, not interface. In this situation, combination of DFT calculation with another type of sampling such as microkinetics and structure prediction technique is an interesting direction. In this talk, I will introduce DFT sampling approaches recently implemented in our group for disorderd heterogeneous solid-solid interfaces and our researches on the inonics at oxide cathode / sulfide electrolyte interfaces in all-solid-state batteries [1-4]. The sampling breakthrough was achieved by the CALYPSO technique [5,6], which allows us to explore a variety of interfacial disordered structures. The approach is compatible to massive parallel calculations with high performance computing resources like “Fugaku”. The sampled interfacial structures enable to examine the chemical potential and potential energy surface of mobile ions around the solid-solid interfaces, which gives a perspective about the interfacial space-charge and electric double layers as well as their relations with the interface ionics. These works were done in collaboration with Dr. Bo Gao, Prof. Yanming Ma, Dr. Randy Jalem, and Dr. Jun Haruyama. The works were partly supported by MEXT as ""Priority Issue (No.5) on Post K computer” and JSPS KAKENHI “Interface IONICS” Grant Number JP19H05815.","" "AMP2: A Package for Automated Ab-initio Calculation for Crystalline Materials","AMP2: A Package for Automated Ab-initio Calculation for Crystalline Materials","ユン ヨン, Miso Lee, Changho Hong, Doyeon Kim, Kanghoon Yim, 館山 佳尚, Seungwu Han","ユン ヨン, Miso Lee, Changho Hong, Doyeon Kim, Kanghoon Yim, 館山 佳尚, Seungwu Han","22nd Asian Workshop on First-Principles Electronic structure Calculation (ASIAN-22)","22nd Asian Workshop on First-Principles Electronic structure Calculation (ASIAN-22)","2019-10-28","","eng","oral_presentation","","","","","","With high accuracy, ab-initio calculation based on the density functional theory (DFT) become essential components of material science in understanding material properties. However, DFT calculations require a deep knowledge of the theoretical background for reliable data, which can be an obstacle for less experienced users. Developing a fully automated package for DFT calculations makes it easier to use DFT calculations, which would greatly increase the use of DFT calculations. Recently, several automation packages have been developed to build material databases such as AiiDa, atomate, pymatgen and aflow. However, these utilities still assume that users have knowledge of theoretical details. Here, we introduce ‘automated ab initio modeling of materials property package’ (AMP2) for fully automating DFT calculations with minimal user interference. Starting from crystalline structure, AMP2 calculates various crystalline properties of the material such as band gap, band structure, density of states, effective mass and dielectric constant using the preset algorithms that incorporate well-established know-hows. In particular, AMP2 identifies the ground-state antiferromagnetic ordering by applying the Ising model, and overcomes the band gap underestimation in semi-local functionals with the help of hybrid functional method. In conclusion, we expect that AMP2 would help to understand material properties and predict new high performance materials. ","" "Genetic Algorithm Based Force Field Parameterization for Lithium-Ion Battery Applications","Genetic Algorithm Based Force Field Parameterization for Lithium-Ion Battery Applications","ガオ シーチャン, 館山 佳尚, 赤木和人","ガオ シーチャン, 館山 佳尚, 赤木和人","計算物質科学人材育成コンソーシアム(PCoMS)シンポジウム 2019","計算物質科学人材育成コンソーシアム(PCoMS)シンポジウム 2019","2019-10-24","","eng","oral_presentation","","","","","","Nowadays, it is widely recognized that the performance of lithium-ion batteries is greatly dependent on the ion transport properties. Many force fields such as AMOEBA, APPLE&P, CHARMM and some force fields based on Drude model have the potential to be applied to LIB applications. However, the mechanism of lithium ion transport in electrolytes remains elusive so far. The reason mainly comes from the lack of appropriate parameters for reliable MD simulations. Force field parameterization is a challenging and time-consuming process, especially in the case of complex potential function and high dimensional parameters. Fortunately, genetic algorithm (GA) is well suited to solve this problem. Therefore, in order to elucidate the mechanism of lithium transport, we have developed a genetic algorithm based force field for the lithium-ion battery applications.","" "Atomic-scale insight into surface morphology and stability of interface between garnet Li7La3Zr2O12 and Li metal from first principles","Atomic-scale insight into surface morphology and stability of interface between garnet Li7La3Zr2O12 and Li metal from first principles","高 博, ハレム ランディ, 館山 佳尚","高 博, ハレム ランディ, 館山 佳尚","2nd World Conference on Solid Electrolytes for Advanced Applications: Garnets and Competitors (Garnet2019)","2nd World Conference on Solid Electrolytes for Advanced Applications: Garnets and Competitors (Garnet2019)","2019-09-24","","eng","oral_presentation","","","","","","Garnet-type Li7La3Zr2O12 (LLZO) is a promising solid electrolyte, which enables the use of Li metal anode to achieve solid-state batteries with higher energy densities. However, the significant issues (e.g. interface reaction, dendrite formation) have been observed in LLZO/Li metal anode interface. Although there are several theoretical and experimental investigations on this interface, the lack of atomic-scale knowledge of interface structures strongly impedes the in-depth understanding of the stability of this interface. Moreover, the interface structures are directly influenced by the surface morphology. Therefore, the surface structure is necessary to be elucidated. Herein, we perform a comprehensive first-principles investigation on this issue. The surface morphology of LLZO and its influence on the stability of LLZO/Li metal interface have been clarified. It is found that in Zr reducing atmosphere, the surface O bonding with Zr easily lose, leading to the formation of ZrO5 polyhedron. The Zr in ZrO5 unit is strongly reduced by Li metal in LLZO/Li interface, inducing the interface degradation. Our calculation results suggest that preserving ZrO6 unit is key for the stability of LLZO/Li interface. This atomic-scale insights provide a new perspective for optimizing interface between LLZO electrolyte and Li metal anode. ","" "DFT studies on ionic and electronic states around electrode/solid-electrolyte interfaces via efficient structure search techniques","DFT studies on ionic and electronic states around electrode/solid-electrolyte interfaces via efficient structure search techniques","館山 佳尚","館山 佳尚","2nd World conference on Solid Electrolytes for Advanced Applications: Garnets and Competitors (Garnet2019)","2nd World conference on Solid Electrolytes for Advanced Applications: Garnets and Competitors (Garnet2019)","2019-09-24","","eng","oral_presentation","","","","","","All solid-state batteries (ASSBs) have been regarded as promising next-generation Li-ion batteries (LIBs). However, high resistance of Li+ transport and low electrochemical stability at the electrode/solid-electrolyte (SE) interface remain crucial bottlenecks for the commercialization. Although interposing a buffer layer onto the interface has been used to mitigate this problem, the fundamental mechanism is still under debate. We have been exploring the atomistic understanding of this interfacial resistance mechanism with DFT-based calculation approaches [1,2]. However, sufficient sampling of the heterogeneous disordered solid/solid interface structures is too cumbersome for deducing any significant statistical and general features. Thus, we utilized the CALYPSO structure prediction technique [3,4] for the solid/solid interface structure search, combining with treatments of mismatch, lateral bulk shift etc. As representative model systems, we applied the above DFT-based calculation techniques to LiCoO2 (LCO), β-Li3PS4 (LPS), and LiNbO3 (LNO) acting as a cathode, a sulfide electrolyte, and a buffer layer, respectively. For the LCO/LPS interfaces, we sampled over 20000 configurations and found several stable disordered structures involving mixing cations and anions, leading to the formation of a reaction layer. On the other hand, Li-ion sites that can be preferentially depleted upon charging always exist around the cathode/SE interfaces irrespective of the interfacial order/disorder. We also found that the interfacial electron transfer is possible for the LCO/LPS interfaces and suppressed by the buffer layer. These results indicated that the dynamic Li-ion depletion is likely to be a major cause that prevents successive Li-ion transport, leading to resistance. In the talk, we will also discuss the related works on anodes/SE interfaces like Li/LLZO interfaces.","" "First-Principles Study on Na+ Ion Transport in Na3SbS4 Solid Electrolyte for All-Solid-State Na Ion Battery","First-Principles Study on Na+ Ion Transport in Na3SbS4 Solid Electrolyte for All-Solid-State Na Ion Battery","TATEYAMA Yoshitaka, JALEM Randy","TATEYAMA Yoshitaka, JALEM Randy","The 2nd World Conference on Solid Electrolytes for Advanced Applications: Garnets and Competitors","The 2nd World Conference on Solid Electrolytes for Advanced Applications: Garnets and Competitors","2019-09-24","","eng","oral_presentation","","","","","","All-solid-state Na ion battery (ASS-NIB) is a battery design conceptualized for the improvement of safety and reliability of conventional Na ion battery, in parallel with the motivation for all-solid state Li ion battery which is a way to improve conventional Li ion battery. One critical component in ASS-NIB is the solid electrolyte which is required to have high ionic conductivity to aid in the fast transport of Na ions between electrodes during the charge-discharge process. Herein, we focused on the Na ion migration behavior in a recently reported sulfide-type solid electrolyte Na3SbS4. By using density functional theory (DFT) calculations, we investigated how defects, halide doping, and possible secondary decomposition phases would impact the overall Na ion migration property of the material. Using nudged elastic band (NEB) method, it was revealed that the Na+ ion migration energies along major crystallographic directions in undoped Na3SbS4 are enormously low (< 0.10 eV), under a vacancy-driven model. Aside from Na vacancy, Na interstitial formation energy is also predicted to be low (~0.15 eV) which suggests that such native defect would likely form part of the description for the long-range bulk inter-diffusion mechanism in Na3SbS4. Meanwhile, halide doping at the S site was determined to generally increase the vibrational jump frequency to a factor of ~1.5 for the conductivity prefactor contribution. However, bulk Na+ ion activation energy is calculated to increase by vacancy trapping effect near the dopant, this leads to a ~3 order of magnitude decrease in the Boltzmann factor for ionic conductivity. Among possible secondary phases, Na2S was found to be beneficial for inter-grain transport because of low Na+ ion migration energy barrier value of 0.28 eV. ","" "LiNi0.5Mn1.5O4正極/EC電解液界面における電解液分子の吸着状態及び酸化分解機構に関する第一原理計算研究","LiNi0.5Mn1.5O4正極/EC電解液界面における電解液分子の吸着状態及び酸化分解機構に関する第一原理計算研究","館山 佳尚, 後瀉啓介, 奥野幸洋","館山 佳尚, 後瀉啓介, 奥野幸洋","第13回分子科学討論会","第13回分子科学討論会","2019-09-17","","jpn","oral_presentation","","","","","","","Density functional theory (DFT) calculations were applied to investigate the stable adsorption structure of ethylene carbonate (EC) on the spinel-structured LiNi0.5Mn1.5O4 (LNMO) surfaces and the initial steps of EC (electro) chemical reactions on the surfaces. DFT molecular dynamics simulations indicated that EC molecules have two characteristic adsorption modes that can explain the experimental observations. Then, we examined several possible pathways of EC decomposition on the LNMO (100) surface and estimated their activation barriers. The results showed that the pristine LNMO (100) surface was inert for the EC decomposition, whereas on delithiated surfaces, twofold-coordinated surface oxygen can serve as active sites for nucleophilic attack on the carbonyl carbon and the methylene group of adsorbed EC molecules. The induction of ring opening of the EC molecule by the former attack, and hydrogen abstraction from the methylene group and subsequent CO2 generation by the latter account for the experimental observaitons." "Density Functional Theory-Based Microkinetic Analysis of Oxidative Coupling of Methane Catalyzed by Pure and Lithium-Doped Magnesium Oxide","Density Functional Theory-Based Microkinetic Analysis of Oxidative Coupling of Methane Catalyzed by Pure and Lithium-Doped Magnesium Oxide","石川 敦之, 館山 佳尚","石川 敦之, 館山 佳尚","EuropaCat2019","EuropaCat2019","2019-08-18","","eng","oral_presentation","","","","","","The oxidative coupling of methane (OCM) has long been studied becuase it is an effective approach to make higher hydrocarbons from natural gas. The reaction mechanism is complicated because it involves both gas-phase and surface-mediated reactions. For the full understanding on the reaction mechanism, theoretical study, especially from atomic or molecular level is helpful. At the same time, macroscopic scale simulation is also important from practical aspect becuase estimation of activity such as CH4 conversion and selectivity of target C2 compounds is needed to discover new catalyst systems. To this aim, we carried out density functional theory (DFT) combined with microkinetics and chemical reactor modeling, as this approach enables the activity and selectivity prediction from atomic or molecular level simulations.","" "Theoretical Study on Termination Dependent Redox Reactivity of Boron-Doped Diamond / Water Interface","Theoretical Study on Termination Dependent Redox Reactivity of Boron-Doped Diamond / Water Interface","館山 佳尚, 飯塚 将太, Keisuke Natsui, Yasuaki Einaga","館山 佳尚, 飯塚 将太, Keisuke Natsui, Yasuaki Einaga","ISE 70th Annual Meeting","ISE 70th Annual Meeting","2019-08-04","","eng","oral_presentation","","","","","","Boron doped diamond (BDD) is a peculiar electrode material, which has wide potential window, low background current, high chemical stability and so on, leading to efficient waste-water treatment and sensor application. Our experimental studies so far showed that BDD electrodes have a variety of redox reaction reactivities depending on the surface termination structures (H-, OH-, O-, F-terminations etc.) and Boron concentrations. The termination dependences are characteristics of BDD (and the other semiconductor electrodes), different from typical metallic and oxide electrodes. However, the atomistic mechanism of the electrochemical reactions at BDD/water interfaces have not been fully understood yet. Recently, the electrochemical properties of H-terminated BDD, OH-BDD and F-BDD were compared with the cyclic voltammogram measurement of anionic, neutral and cationic redox targets based on catechol [1]. It is then observed that the oxidation and reduction current densities decrease for F-BDD, compared to H- and OH-BDD. Especially, the current density for the anionic target was significantly suppressed for F-BDD. Also, the oxidation potential for each target monotonously shifted toward the positive direction from H-BDD to F-BDD. To understand the termination dependence of the BDD/water interfaces, we carried out (i) density functional theory based molecular dynamics (DFT-MD) simulations of water interfaces of the H-, OH- and F-BDD electrodes, and (ii) post-analysis on the basis of the space-charge and electric double layers as well as Fermi golden rule [2]. Since accurate and efficient sampling of solid-liquid interface states is still challenging. we implemented highly-parallelized DFT-MD code called “stat-CPMD” based on the open source CPMD, and utilized the K-computer, a flagship supercomputer in Japan. ","" "Density functional theory-based microkinetic analysis of oxidative coupling of methane catalyzed by pure and lithium-doped magnesium oxide","Density functional theory-based microkinetic analysis of oxidative coupling of methane catalyzed by pure and lithium-doped magnesium oxide","石川 敦之, 館山 佳尚","石川 敦之, 館山 佳尚","The 8th Asia Pacific Congress on Catalysis","The 8th Asia Pacific Congress on Catalysis","2019-08-04","","eng","oral_presentation","","","","","","The oxidative coupling of methane (OCM) has long been studied becuase it is an effective approach to make higher hydrocarbons from natural gas. The reaction mechanism is complicated because it involves both gas-phase and surface-mediated reactions. For the full understanding on the reaction mechanism, theoretical study, especially from atomic or molecular level is helpful. At the same time, macroscopic scale simulation is also important from practical aspect becuase estimation of activity such as CH4 conversion and selectivity of target C2 compounds is needed to discover new catalyst systems. To this aim, we carried out density functional theory (DFT) combined with microkinetics and chemical reactor modeling, as this approach enables the activity and selectivity prediction from atomic or molecular level simulations.","" "DFT sampling approach of interface and surface processes in battery and catalyst","DFT sampling approach of interface and surface processes in battery and catalyst","館山 佳尚","館山 佳尚","CPMD Meeting 2019","CPMD Meeting 2019","2019-07-22","","eng","oral_presentation","","","","","","Interface and surface processes in energy and environmental devices such as batteries and catalysts largely govern their performance and stability. To understand the roles of such processes, however, typical static geometry optimization or even molecular dynamics (MD) based on DFT framework does not work well often due to the multiscale character. On the other hand, parameter-based methods such as classical MD are still insufficient because their parameters are usually fitted with bulk properties, not interface and surface. In this situation, combination of DFT calculation with another type of sampling such as microkinetics and structure prediction technique is an interesting direction. In this talk, I will introduce some DFT sampling approaches recently implemented in our group for multiple surface processes in catalytic reactions as well as solid/solid interface characterization in all-solid-state batteries [1,2]. These calculations with a high-throughput technique demonstrate how they solve rather longstanding issues in the battery and catalyst fields. I also point out that high performance computing resources help these predictive computational approaches and generation of a large data-set of interface and surface processes. These works were done in collaboration with Dr. Atsushi Ishikawa, Dr. Bo Gao, Prof. Yanming Ma, and Dr. Randy Jalem.","" "Effects of Magnesium-Organo-Haloaluminate complex in Magnesium Ion Battery electrolytes: A Car-Parrinello Molecular Dynamics (CPMD) Study","Effects of Magnesium-Organo-Haloaluminate complex in Magnesium Ion Battery electrolytes: A Car-Parrinello Molecular Dynamics (CPMD) Study","チョーダリー アシュ, 袖山 慶太郎, 館山 佳尚","チョーダリー アシュ, 袖山 慶太郎, 館山 佳尚","CPMD Meeting 2019","CPMD Meeting 2019","2019-07-22","","eng","oral_presentation","","","","","","An ongoing challenge for magnesium ion batteries (MIB) is finding electrolytes efficient for Mg2+ deposition/dissolution. Magnesium-organo-haloaluminate complex are found one of such electrolytes which show reversible electrodeposition1. However, the less is known about the equilibria regulating in such Mg-organo-haloaluminate complexes and the functional species responsible for the deposition/dissolution of such electrolyte complex2. We carried out ab-initio Car-Parrinello molecular dynamics samplings of different components of the complex and related species in solvent Tetrahydrofuran (THF): (i) EtMgCl + AlCl3 in 42 THF ; (ii) MgCl+ + EtAlCl3- in 42 THF ; (iii) MgCl2 + EtAlCl2 in 42 THF . The edge length of each simulation box is 18.23 Å. We employed the dispersion corrected PBE-D2 functional. After the equilibration, statistical averages were computed from trajectories of at least 60 ps in length in NVT ensemble at T=300K. The electronic wave function was quenched to the Born–Oppenheimer surface about every 1 ps in order to maintain adiabaticity. We then studied the structural, vibrational properties and projected density of states (PDOS) of the systems. We found system (ii) MgCl+ + EtAlCl3- in 42 THF as the most stable among the three systems studied here. The vibrational spectra shift observed for THFs in the solvation shell of Mg-ion moieties and Al-ion moieties are quite different, mainly provide different red shift for the -C-O- frequencies for solvation shell THFs. The structural properties shed a light about the existing ambiguity in the coordination of Magnesium ion in such solutions. We found via PDOS that few THFs plays an important role in the electron transfer process. As the important factor for the electrolyte is the anodic stability therefore the possibility of broken THF are also investigated in a great detail.","" "第一原理計算からみた蓄電池界面のイオン・電子状態","第一原理計算からみた蓄電池界面のイオン・電子状態","館山 佳尚","館山 佳尚","第74回固体イオニクス研究会","第74回固体イオニクス研究会","2019-07-12","","jpn","oral_presentation","","","","","","","全固体電池は、従来の電解液系リチウムイオン電池と比べ、高いエネルギー密度と安定性が期待されている。最近、重大なボトルネックであった固体電解質内のイオン電導度に関して、特に硫化物系電解質を中心に大きなブレークスルーがあった。これにより硫化物系全固体電池に対しては、界面におけるイオン移動抵抗の軽減や電気化学的安定性の担保が、残された主要課題となっている。一方、電気化学的安定性に優れていると考えられる酸化物系全固体電池についても、高イオン電導材料の探索に加えて、界面における接合性の担保が課題となっている。このように、全固体電池の実用化に向けて、電極-固体電解質界面の原子スケールでの理解と制御が中心的な重要課題となっている。 イオン電導に関する界面抵抗(電荷移動抵抗)については、これまで硫化物系を中心に様々な機構が提案されてきた。高田らは遷移金属酸化物正極ー硫化物電解質の間に酸化物の緩衝層を導入することで界面抵抗が著しく減少することを発見した。この現象は様々な緩衝層で共通にみられることから、界面抵抗の主要因は緩衝層材料に依存した化学的なものではなく、界面付近のイオン分布の減少による空間電層の形成という物理的効果であるという提案を行ってきた。一方、辰巳砂らはエネルギー分布型X線分析により界面近傍の元素分布を測定し、界面を横切るイオン移動(例えば正極のCoの硫化物電解質側への流出)が数十ナノメートルスケールで存在すること、緩衝層によりその分布が狭まることを発見した。これらを界面の反応層形成と考え、界面抵抗の主要因として考えた。また、入山らは界面におけるゆがみ緩和の効果を指摘している。 近年、透過型電子顕微鏡などの界面計測技術は著しい発展を遂げているものの、材料内に埋もれた構造無秩序性のあるヘテロな固固界面のその場観察・オペランド観察はいまだに困難な状況にある。このような状況下で、”構成度”な原子スケールの計算科学シミュレーション解析は重要な役割を果たす。実験との比較が難しい状況で理論的予測を行うためには”高精度”が必須となる。 我々は密度汎関数理論(DFT)をベースにした第一原理計算を用いてこの問題に取り組んできた。その中で、単に第一原理計算を適用するだけでなく、「構造無秩序性のあるヘテロな固固界面」に対する一般的な取り扱い手法の確立・開発を行ってきた。例えば格子不整合、歪みの緩和と残留歪み、格子スライド、界面再構成、イオン交換等の考慮方法を提案してきている。また、全固体電池内現象を取り扱ううえで完全放電状態、充電初期、充電終了状態、放電初期などを区別することの重要性も指摘してきた。さらに、固固界面を電気化学と半導体物理の両者の観点から統一的に解釈する試みも行ってきている。" "Structure Search and Property Analysis of Interfaces between Cathode and Solid Electrolyte in All-Solid-State Battery via DFT-CALYPSO Method","Structure Search and Property Analysis of Interfaces between Cathode and Solid Electrolyte in All-Solid-State Battery via DFT-CALYPSO Method","高 博, ハレム ランディ, Yanming Ma, 館山 佳尚","高 博, ハレム ランディ, Yanming Ma, 館山 佳尚","The 11th International Conference on the Science and Technology for Advanced Ceramics (STAC-11)","The 11th International Conference on the Science and Technology for Advanced Ceramics (STAC-11)","2019-07-09","","eng","oral_presentation","","","","","","All-Solid-state batteries (ASSBs) is of great interest because of its high safety and high energy density in comparison to traditional liquid electrolytes based batteries. However, there is a crucial issue about the interface resistance between the cathode and electrolyte in many ASSBs, which hinders the performance of batteries. To understand the microscopic mechanism of the interface resistance, we systemically investigate the interface configurations between LiCoO2 cathode and Li3PS4 sulfide solid electrolyte using CALYPSO structure prediction approach[1]. Several efficient techniques have been applied in our method, including an automatic toolkit for searching matched superlattice, a structure generation method including the lattice displacement, and PSO algorithm. For the obtained energetically favorable structures, we calculated the electronic states and Li vacancy formation energies. We found that the interfacial layer is formed accompanied by the cation mixing (Co ↔ P exchange) and anion mixing (O ↔ S exchange). We then revealed that there are interfacial Li sites where preferential Li depletion can occur upon charging, even in very disordered interfaces. Besides, the present study demonstrated how to explore the structures of solid-solid interfaces at the atomic scale.","" "DFT computational study on stability and ion diffusion in Na3SbS4 solid electrolyte for all-solid-state batteries","DFT computational study on stability and ion diffusion in Na3SbS4 solid electrolyte for all-solid-state batteries","TATEYAMA Yoshitaka, JALEM Randy","TATEYAMA Yoshitaka, JALEM Randy"," the 22nd International Conference on Solid State Ionics (SSI-22)"," the 22nd International Conference on Solid State Ionics (SSI-22)","2019-06-16","","eng","oral_presentation","","","","","","Like Li-ion battery, increasing demand for highly safe energy storage has driven many researches into rethinking the current design of a typical Na-ion battery. All-solid-state Na-ion battery (ASS-NIB) is now becoming strongly sought as promising alternative, especially over conventional and even all-solid-state Li-ion batteries. One crucial component in ASS-NIB is the solid electrolyte which is required to be highly stable and of high ionic conductivity. In this study, we performed theoretical study based on density functional theory (DFT) calculations for the Na3SbS4 compound which is a recently reported solid electrolyte for ASS-NIB application. We evaluated the electrolyte’s stability in terms of anode/cathode contact and the Na ion transport property behavior. Based from grand potential phase diagram and chemical potential analyses (see Fig. 1b), at the cathode-electrolyte interface with possible layered compound cathodes (i.e., Na[TM]O2, where TM = {V, Cr, Mn, Fe, Co, Ni}), some non-Na elements have the thermodynamic driving force to migrate across, which can lead to interface atomic rearrangement, interface disordering and/or decomposition. We also predicted using kinetic modelling that stresses at the anode-electrolyte interface at typical electrodeposition surface roughness would lead to the initiation of Na dendrites. By nudged elastic band method, we found enormously low Na ion migration energies (<0.10 eV) for a vacancy-driven mechanism in the local pathways of bulk Na3SbS4. The effect of halide doping on ion migration energy and the possible role of secondary phases for inter-grain transport will be presented as well. Finally, with the aforementioned new detailed insights, possible strategies towards developing practical ASS-NIB systems will be discussed. ","" "DFT Studies on Li-Ions Around Electrode-Solid Electrolyte Interfaces via Efficient Structure Search Techniques","DFT Studies on Li-Ions Around Electrode-Solid Electrolyte Interfaces via Efficient Structure Search Techniques","館山 佳尚, 高 博, ハレム ランディ, Yanming Ma","館山 佳尚, 高 博, ハレム ランディ, Yanming Ma","2019 MRS Spring Meeting & Exhibit","2019 MRS Spring Meeting & Exhibit","2019-04-22","","eng","oral_presentation","","","","","","Solid-state batteries (SSBs) have been regarded as promising next-generation Li-ion batteries (LIBs), and promising solid electrolytes (SEs) with higher Li-ion conductivities have been found. However, the high interfacial resistance of Li-ion transport at the electrode-SE interface remains a crucial bottleneck. Although We have been exploring the atomistic understanding of this interfacial resistance mechanism with DFT-based calculation approaches [2,3]. So far we have devised some systematic ways for the solid-solid interfaces and discussed possible origins such as the space-charge layer and the reaction layer. However, the sufficient sampling of the solid-solid interface configurations is too cumbersome for deducing any significant statistical and general features of the interfacial Li-ion transport. Hence, we utilized the CALYPSO structure prediction method [4,5] as a calculation technique for the interface structure search, to be combined with mismatch treatment, lateral shift etc. Here as representative model systems, we applied the above DFT-based calculation techniques to LiCoO2 (LCO), β-Li3PS4 (LPS), and LiNbO3 (LNO) acting as a cathode, a sulfide electrolyte, and a buffer layer, respectively, For the LCO/LPS interfaces, we sampled over 20000 configurations and found several stable disordered structures involving cation and anion exchange, leading to the formation of a reaction layer. On the other hand, Li-ion sites that can be preferentially depleted upon charging always exist around the cathode-SE interfaces irrespective of the interfacial order/disorder. Therefore, we conclude that the dynamic Li-ion depletion is likely to be a major cause that prevents successive Li-ion transport, leading to the resistance. Through investigating the buffer layer effects and the interfacial electronic states, we also deduced a probable origin for the interfacial Li depletion and a mean to suppress this problematic behavior. In the talk, we will also discuss the related works on anodes and SEI interfaces.","" "NO + CO Reaction on Rh Surface: DFT Investigation Combined with Microkinetic Analysis","NO + CO Reaction on Rh Surface: DFT Investigation Combined with Microkinetic Analysis","石川 敦之, 館山 佳尚","石川 敦之, 館山 佳尚","Spring 2019 ACS National Meeting","Spring 2019 ACS National Meeting","2019-03-30","","eng","oral_presentation","","","","","","In the NO + CO catalytic reaction on Rh(111), it is known from experiments that N2O and N2 are formed at low and high reaction temperatures, respectively, although the mechanism has not been fully understood. Here, we clarified its detailed mechanism using ab initio density functional theory (DFT) and microkinetic analysis. We considered that the catalytic cycle consists of following steps: NO dissociation, N2O formation, N2 formation (via N−N recombination or N2O decomposition), and CO2 formation. Their reaction energies and activation barriers were evaluated by DFT calculations and were then employed for the microkinetics and reactor simulation. We then demonstrated that N2O and N2 are mainly formed at low and high temperatures, respectively, in agreement with experiments. This is because (i) N2O formation has a lower activation barrier than that of N2 formation and thus has a faster rate at low temperature, whereas N2 formation is dominant at high temperature because of the large exothermicity, and (ii) at a higher temperature, NO dissociation occurs more and thus sufficient amount of surface N atom is provided, accelerating N + N → N2. This study demonstrated that to analyze the catalytic reactions in a wide temperature range the combination of the DFT calculation, surface microkinetics, and reactor simulation plays a crucial role.","" "第一原理計算と微視的反応速度論に基づいた理論計算によるメタン酸化カップリングの活性および選択性の理論予測","第一原理計算と微視的反応速度論に基づいた理論計算によるメタン酸化カップリングの活性および選択性の理論予測","石川 敦之, 館山 佳尚","石川 敦之, 館山 佳尚","第123回触媒討論会","第123回触媒討論会","2019-03-20","","jpn","oral_presentation","","","","","","","本発表では、物質の構造情報から反応速度論的情報を得ることのできる第一原理計算と、反応速度論さらには化学工学のシミュレーション技法を融合することでどのような材料に対しても触媒活性を予測することのできる手法のメタン触媒への適用結果を報告する。" "First-principles study on electrode – solid electrolyte interfaces in solid-state battery via efficient structure prediction method","First-principles study on electrode – solid electrolyte interfaces in solid-state battery via efficient structure prediction method","高 博, ハレム ランディ, Yanmimg Ma, 館山 佳尚","高 博, ハレム ランディ, Yanmimg Ma, 館山 佳尚","APS March Meeting 2019","APS March Meeting 2019","2019-03-04","","eng","oral_presentation","","","","","","Understanding the origin of high interfacial resistances between electrodes and solid-electrolytes is crucial for commercial application of solid-state batteries (SSBs). [Chem. Mater. 26, 4248-4255] [ACS Appl. Mater. Interfaces 9, 286-292]. Here we utilized the CALYPSO structure prediction method [Physical Review B 82, 094116] to investigate the interface structures between LiCoO2 cathode and β-Li3PS4 sulfide electrolyte. About 20000 configurations are sampled to search the stable interface structures. The results show that the interfacial reaction layer is formed accompanied by the cation mixing and anion mixing. It is confirmed that the preferential Li depletion can occur at interface upon charging, even in very distorted region. Furthermore, CALYPSO interface structure prediction method can be applied to the solid-solid interface systems beyond the SSBs.","" "Finding Novel Fast Ionic Conductors Using Combined Techniques from Density Functional Theory and Materials Informatics","Finding Novel Fast Ionic Conductors Using Combined Techniques from Density Functional Theory and Materials Informatics","ハレム ランディ, 金森研太, 竹内 一郎, 館山 佳尚, 中山 将伸","ハレム ランディ, 金森研太, 竹内 一郎, 館山 佳尚, 中山 将伸","APS March Meeting 2019","APS March Meeting 2019","2019-03-04","","eng","oral_presentation","","","","","","Computational new material search and discovery is an ongoing hot topic for research in various fields of applications. In here, we show our recent works related to efficient computational methods for finding novel fast ionic conductors for potential use in battery applications. One topic deals with our proposed search framework based on a Bayesian optimization algorithm with a kernel definition that is general for high dimension of material descriptors, coupled to a first-principles density functional theory (DFT) method to calculate ion migration energy barriers (Eb) over chemical search spaces of oxide materials (Eb serves as a search criterion) (Sci. Rep. 2018, 8, 5845). The second part will show our formulation of descriptors for crystalline solids which are derived from chemical element literature data and real feature values from atom-centered Voronoi partitioning (STAM 2018, 19, 231). We validated the scheme in terms of whether learning is achievable on various DFT-calculated properties such as cohesive energy, material density, electronic band gap energy, and convex hull decomposition energy.","" "Computational Study on Possible High Potential Ilmenite Type Na1TMO3 (TM=3d, 4d Transition Metals) Cathodes Based on Oxygen Redox Reaction","Computational Study on Possible High Potential Ilmenite Type Na1TMO3 (TM=3d, 4d Transition Metals) Cathodes Based on Oxygen Redox Reaction","アルアサディ フセインナシーフモハマド, Masashi Okubo, Atsuo Yamada, 館山 佳尚","アルアサディ フセインナシーフモハマド, Masashi Okubo, Atsuo Yamada, 館山 佳尚","International Battery Association 2019 (IBA2019)","International Battery Association 2019 (IBA2019)","2019-03-03","","eng","oral_presentation","","","","","","Na is a probable alternative for Li in rechargeable batteries due to its lower cost and higher abundance. Na, however, has a larger ionic radius and smaller ionisation potential compared to Li. Given these shortcomings, to design a Na ion based cathode material comparable in performance to Li, all mechanisms that may increase the capacity and voltage beyond that of the current limits should be carefully fine-tuned [1]. Here, through comprehensive density functional calculations, we screened the full range of ternary hexagonal layered compounds with ilmenite structure (space group 158) that consist of Na, O and 4d or 3d transition elements (TM) in search for candidates with a possibly higher operating voltage. The investigated TMs were V, Cr, Mn, Fe, Co, Ni, Nb, Mo, Tc, Ru, Rh, Pd and Ag. In the calculations, we treated the exchange-correlation interaction of the 3d TM containing compounds with hybrid HSE03 functional to account for the strong correlation effects. For 4d TM cases, on the other hand, we found that the GGA+U formalism sufficed for describing the band structure accurately. We, furthermore, found that a Ueff value of 2 eV could particularly reproduce the electrochemical potential of Na extraction in NaxRuO3 compound [2], which we then utilised for the rest of 4d TM containing compounds. Figures 1(a) and (b) show the structure of the sodiated compound Na1TMO3 (R-3) and the desodiated compound Na0.5TMO3 (P-31m) respectively. In the ilmenite type Na1TMO3, due to the R-3 symmetry, O ions are coordinated by two TM and two Na ions and two vacant sites. In this case, O under-coordination elevates the unhybridised or orphaned portion of O 2p states closer to the Fermi level. High O electronic population near the Fermi level facilitates greater O ","" "Theoretical Study on Redox Reactions at Boron-Doped Diamond / Water Interfaces","Theoretical Study on Redox Reactions at Boron-Doped Diamond / Water Interfaces","飯塚 将太, Zdenek Futera, Takeshi Watanabe, Keisuke Natsui, Yasuaki Einaga, 館山 佳尚","飯塚 将太, Zdenek Futera, Takeshi Watanabe, Keisuke Natsui, Yasuaki Einaga, 館山 佳尚","JST-ACCEL「ダイヤモンド電極の物質科学と応用展開」国際シンポジウム","JST-ACCEL「ダイヤモンド電極の物質科学と応用展開」国際シンポジウム","2019-03-06","","eng","oral_presentation","","","","","","Boron doped diamond (BDD) is a peculiar electrode material, which has wide potential window, low background current, high chemical stability and so on. BDD electrodes also show a variety of reactivities, depending on the surface termination (-H, -OH, -O, -F etc.) and Boron concentration. These differentiate BDD from the typical metallic and oxide electrodes. However, the microscopic mechanisms of the chemical and electrochemical reactions at BDD/water interfaces have not been fully understood yet due to the difficulty in in-situ or operando measurements of the interface processes. To understand such atomistic behaviors at the BDD/water interfaces, we have been carrying out computational analyses of the interfacial redox reactions by use of density functional theory based molecular dynamics (DFT-MD) simulations. Accurate and efficient sampling of solid-liquid interface states is still challenging. Nevertheless, we implemented highly-parallelized DFT-MD code called “stat-CPMD” and utilized the K-computer, a flagship supercomputer in Japan. We obtained various equilibrium structures (trajectories) of BDD/water interfaces with different terminations, and calculated the electronic properties such as the band alignment at the interfaces, the band bending tendency and the interface states. These analyses demonstrated the reductive character of H-terminated BDD and the oxidative features of OH-, O- and F-terminated BDD [1,2,3]. Combining the experimental observations of cyclic voltammogram etc., we could propose the probable mechanisms on the electronic and atomic scales. We have also examined the reactions involving the termination atoms, which explains the bias dependence as well as the radical generation mechanisms [4]. Such comprehensive theoretical studies will provide a novel perspective of BDD electrodes as well as a unified fundamental aspect of solid-liquid interfaces.","" "First -principles sampling simulation approaches to battery science and thechnology","First -principles sampling simulation approaches to battery science and thechnology","館山 佳尚","館山 佳尚","第1回R-CCS国際シンポジウム","第1回R-CCS国際シンポジウム","2019-02-18","","eng","oral_presentation","","","","","","Development of next-generation battery is a most important issue in modern society. For emerging technologies such as electric vehicle and smart grid, batteries with higher energy and power densities, higher safety and longer durability are needed. From the viewpoint of materials science, elucidation of all electronics and atomic processes in the battery is essential. However, the in-situ experimental observations are still difficult and many problems remain unsolved. Then, we have addressed understanding the battery microscopic mechanisms by means of first-principles sampling simulation approaches based on density functional theory (DFT) calculations of the electronic states with reasonable accuracy. By adding the multiple parallelisation functions to a DFT molecular dynamics (MD) open source “CPMD” [1], we constructed “stat-CPMD extension” for efficient sampling and free energy profile calculation of chemical and redox reactions on the K computer. The stat-CPMD code showed FLOPS efficiency over 30% and SIMD ratio over 70% in the best cases. We then addressed long-standing issues of the SEI (solid electrolyte interphase) formation and properties at anode – organic electrolyte interfaces, which really determines the performance and the reliability of the battery. Besides, we have investigated the electrochemical and transport properties of a new class of electrolyte, “highly-concentrated electrolyte”, emerging recently. Regarding the SEI issue, we found a novel mechanism of the VC additive effect on the initial reductive decomposition of EC solvent [2], and then proposed a probable subsequent mechanism with the decomposed products toward the SEI formation at the electrode – electrolyte interface [3,4], which overturns the conventional understandings. For the latter, we elucidated origins of the unusual electrochemical stability and excellent ion transport in superconcentrated electrolytes [5-9]. These findings via DFT sampling simulations provide new perspectives for the battery science and technology.","" "DFT sampling approaches to microscopic interfacial processes in batteries and catalysts","DFT sampling approaches to microscopic interfacial processes in batteries and catalysts","館山 佳尚","館山 佳尚","Computational Sciences Workshop 2019 (CSW2019)","Computational Sciences Workshop 2019 (CSW2019)","2019-01-16","","eng","oral_presentation","","","","","","Interfacial and surface processes in energy and environmental devices such as batteries and catalysts largely govern their performance, robustness and stability. To understand such processes on the microscopic scale, typical static DFT calculations no longer work well, and their novel combinations with sampling or multi-scale techniques such as Marcus theory, thermodynamic integration, microkinetics, structure search etc. as well as MD and MC, is crucial. In this talk, I will introduce several DFT sampling approaches recently implemented in our group for redox, catalytic and ionic processes [1-7], and demonstrate how they solve rather longstanding issues in the battery and catalyst fields. I’d also point out that high performance computing resources help these predictive computational approaches very much.","" "Revisiting Grignard reagent based electrolytes in magnesium-ion battery : a first-principles study","Revisiting Grignard reagent based electrolytes in magnesium-ion battery : a first-principles study","チョーダリー アシュ, 袖山 慶太郎, 館山 佳尚","チョーダリー アシュ, 袖山 慶太郎, 館山 佳尚","ポスト「京」重点課題5 第5回公開シンポジウム","ポスト「京」重点課題5 第5回公開シンポジウム","2018-12-11","","eng","oral_presentation","","","","","","Magnesium-ion batteries (MIBs) have gained considerable attention as an alternative energy storage to Li-ion batteries in the past few decades. Grignard reagent (R-Mg-X: X=halogen) with ether has been one of the most studied and efficient solutions for MIB. However, the microscopic behaviours in the electrolyte solution are still under debate. To gain insight of the solvation on the atomic scale, we performed the first-principle molecular dynamics samplings of such MIB electrolytes using the CPMD code. The study was also motivated for understanding the fundamental mechanisms of electrolytes for 2+ cation and the underlying differences instead of 1+ cation. We carried CPMD simulations of a single R-Mg-X (where R=Methyl, Ethyl and Phenyl) in different cubic boxes with 44 tetrahydrofuran(THF) molecules. We employed the dispersion corrected PBE-D2 functional. After the equilibration, statistical averages were computed from trajectories of at least 40 ps in length in NVT ensemble at T=300K. The electronic wave function was quenched to the Born–Oppenheimer surface about every 1 ps in order to maintain adiabaticity. We studied the solvation shell structural, vibrational and transport properties for the Grignard reagent based electrolytes dissolved in tetrahydrofuran (THF). The compatibility of electrolyte for reversible dissolution/deposition of Mg2+ is the most important factor to determine Coulombic efficiency of the battery. Therefore, the solvation structure of R-Mg-X in THF is studied through radial distribution functions(RDFs) and vibrational shift in power spectra. The strong solvation of Mg2+ with THF is revealed through the RDFs well-structured peaks. The RDFs differences for different R groups in R-Mg-X (R=Methyl, Ethyl and Phenyl) shows that R=Phenyl, has most closely packed solvation shell and the order of such packing is Ph>Me>Et. ","" "サブ課題B「電解液及び界面課程のシミュレーションに向けたコード開発と応用」","サブ課題B「電解液及び界面課程のシミュレーションに向けたコード開発と応用」","館山 佳尚","館山 佳尚","ポスト「京」重点課題5 第5回公開シンポジウム","ポスト「京」重点課題5 第5回公開シンポジウム","2018-12-11","","jpn","oral_presentation","","","","","","","1:現実的な課題(産業課題など)に適用可能な計算手法・プログラム開発 2: 二次電池系の最重要問題解明への取り組み " "重点課題5インフォマティクス活用WGについて","重点課題5インフォマティクス活用WGについて","館山 佳尚","館山 佳尚","ポスト「京」重点課題5 第5回公開シンポジウム","ポスト「京」重点課題5 第5回公開シンポジウム","2018-12-11","","jpn","oral_presentation","","","","","","","重点課題5ではエネルギー変換・エネルギー貯蔵・物質変換でデータ駆動型AI技術を活用するためのインフォマティクス活用ワーキンググループ(Informatics Application Working Group: IA-WG)を設置し、エネルギー問題への積極的活用の可能性を組織的に検討する。" "Development of Polarizable Force Field for Lithium-Ion Battery Applications","Development of Polarizable Force Field for Lithium-Ion Battery Applications","ガオ シーチャン, 赤木和人, 館山 佳尚","ガオ シーチャン, 赤木和人, 館山 佳尚","ポスト「京」重点課題5 第5回公開シンポジウム","ポスト「京」重点課題5 第5回公開シンポジウム","2018-12-11","","eng","oral_presentation","","","","","","For the well-known lithium battery, despite the progress in macroscopic performance recent years, the microscopic mechanism is still unclear. In attempt to reveal bottlenecks in lithium battery, even find the feasible improvement for the next generation battery designs, a polarizable force field is developed and elaborated. Basing on the nondominated sorting genetic algorithm, parameters were optimized by matching the atomic forces and potential energies for small systems. MD simulation for large systems, which is designed aiming at reproduction of rev-vdw-DF2 grade calculation, gives satisfied results compared with experimental values.","" "Theoretical Study on Termination Dependent Redox Reactivity of Boron Doped Diamond / Water Interface","Theoretical Study on Termination Dependent Redox Reactivity of Boron Doped Diamond / Water Interface","飯塚 将太, 夏井敬介, 栄長泰明, 館山 佳尚","飯塚 将太, 夏井敬介, 栄長泰明, 館山 佳尚","2018 Materials Research Society Fall Meeting","2018 Materials Research Society Fall Meeting","2018-11-25","","eng","oral_presentation","","","","","","Boron doped diamond (BDD) electrode has several unusual characteristics for electrocatalysis and sensor applications. Recently, the cyclic voltammogram measurement showed that the redox reactivity of BDD significantly depends on the termination. To understand the mechanisms, we carried out density-functional theory based molecular dynamics studies on hydrogenated, oxidized and fluorinated BDD interfaces with bulk water. We then found that the interfacial band offset between BDD and water depends on the termination. If the band edge pinning regime holds, the results indicated that the space-charge layer plays a crucial role, partially with the electric double layer, for the charge transfer at the semiconductor / liquid interfaces under bias.","" "Surface Orientation Dependence of Oxygen Vacancy and Ni/Li Cation Mixing Defects Formation in Li(Ni0.8Co0.1Mn0.1)O2 Cathode Materials","Surface Orientation Dependence of Oxygen Vacancy and Ni/Li Cation Mixing Defects Formation in Li(Ni0.8Co0.1Mn0.1)O2 Cathode Materials","シュクリ ガネス, ハレム ランディ, 館山 佳尚","シュクリ ガネス, ハレム ランディ, 館山 佳尚","2018 Materials Research Society Fall Meeting","2018 Materials Research Society Fall Meeting","2018-11-25","","eng","oral_presentation","","","","","","Layered Ni-rich Li(NixMnyCoz)O2(x≧0.5, x+y+z=1) or NCM has been considered as one of the most promising candidates for the next-generation Li-ion battery cathodes because of its high energy density. However, its commercial usage is still hindered partly due to the following two critical issues: (1) safety issue that closely relates to significant NCM lattice oxygen release during operation, (2) capacity fading due to the irreversible layered to spinel/rock-salt phase transformation triggered by Ni/Li mixing defect formation [1]. Herein, by means of density functional theory (DFT)-based calculations we study the aforementioned oxygen release phenomena by examining the oxygen vacancy (Ovac) formation energy, taking Li(Ni0.8Mn0.1Co0.1)O2 or NCM811 as the representative of Ni-rich NCM. We also investigate the Ni/Li mixing defect formation at surface and near-surface regions of NCM811.","" "Elucidation of reaction mechanism at the anode/electrolyte interface in Mg(TFSA)2-based electrolytes","マグネシウム二次電池負極/ Mg(TFSA)2系電解質界面におけるアノード反応機構解明","トウルソン フィロラ, 服部将司, 山本健太郎, 万代俊彦, 松井雅樹, 館山 佳尚, 内山智貴, 竹口竜弥, 金村聖志, 内本喜晴","トウルソン フィロラ, 服部将司, 山本健太郎, 万代俊彦, 松井雅樹, 館山 佳尚, 内山智貴, 竹口竜弥, 金村聖志, 内本喜晴","第59回電池討論会","第59回電池討論会","2018-11-27","","jpn","oral_presentation","","","","","","","Magnesium rechargeable batteries have much attention for next generation batteries because of the high theoretical volumetric capacity, safety, and abundance of magnesium metal anode. For the further development of electrolyte of magnesium batteries, the reaction mechanism at electrolyte/magnesium metal interface should be elucidated. In this study, we examined the electronic and local structures reaction using operando soft X-ray absorption spectroscopy for understanding the mechanism of magnesium deposition/dissolution reactions." "Efficient search of novel ion conductive ceramics by combining first-principles calculations and materials informatics","Efficient search of novel ion conductive ceramics by combining first-principles calculations and materials informatics","ハレム ランディ, 金森研太, 竹内一郎, 館山 佳尚, 中山 将伸","ハレム ランディ, 金森研太, 竹内一郎, 館山 佳尚, 中山 将伸","The 22nd International Symposium on Batteries, Fuel Cells, and Capacitors - The 59th Battery Symposium in Japan ","The 22nd International Symposium on Batteries, Fuel Cells, and Capacitors - The 59th Battery Symposium in Japan ","2018-11-27","","eng","oral_presentation","","","","","","Herein we present our recent works related to efficient computational search/screening of novel fast ionic conductors which are important technological materials for energy conversion and storage application. The first part of the talk will tackle on our developed general representation scheme for crystalline solids (i.e., descriptors), derived from Voronoi tessellation features and elemental/chemical property data, for potential application in large-scale material exploration and discovery of battery materials. The second part will introduce our approach on computational screening using Bayesian-optimization-driven first principles DFT calculation, demonstrating it on a chemical search space with Li-/Na-containing tavorite-type compounds and with computation-intensive material properties as search criteria (eg., ion migration energy). We also highlight the use of transfer learning under the Bayesian optimization scheme as a way to further improve search efficiency.","" "First-principles molecular dynamics simulations on concentrated electrolytes for Na-ion batteries","第一原理MD計算によるナトリウムイオン電池用高濃度電解液の電子状態解析","渡部絵里子, 袖山 慶太郎, 山田裕貴, 館山 佳尚, 山田淳夫","渡部絵里子, 袖山 慶太郎, 山田裕貴, 館山 佳尚, 山田淳夫","第59回電池討論会","第59回電池討論会","2018-11-27","","jpn","oral_presentation","","","","","","","Concentration of electrolytes is a key parameter to achieve battery with high stability, operating voltage, rate-performance and/or safety. Previous theoretical calculations have suggested that the change in the electronic structure is essential to explain several functionalities of highly-concentrated (HC) electrolyte. The changes are usually induced by the peculiar solution structure, but the detailed mechanisms underneath have not been well understood so far. In order to unveil the relationship between solution structure and electronic states, we carried out first-principles Car-Parrinello molecular dynamics sampling study. It was demonstrated that aggregation of anion and alkali-ions lead to downshift of orbital energies located on anions." "Surface orientation dependence of oxygen vacancy and cation exchange in Li(NixCoyMnz)O2 cathode materials","層状構造を持つLi(NixCoyMnz)O2正極材料の表面欠陥に関する第一原理計算解析","シュクリ ガネス, ハレム ランディ, 館山 佳尚","シュクリ ガネス, ハレム ランディ, 館山 佳尚","第59回電池討論会","第59回電池討論会","2018-11-27","","jpn","oral_presentation","","","","","","","Layered Li(NixMnyCoz)O2 (x≧0.5, x+y+z=1) or Ni-rich NCM has been considered as a promising candidate for the next-generation Li-ion battery cathode because of its high energy density. However, its commercial usage is still hindered partly due to (1) safety issue associated with significant NCM lattice oxygen release during operation and (2) capacity fading by the irreversible layered to spinel/rock-salt phase transformation triggered by Ni/Li mixing. Here, using density functional theory (DFT) calculations, we investigated the aforementioned defects formation preference, depending on the surface orientation. Especially, we focused on the defects at surface and near-surface regions of Li(Ni0.8Co0.1Mn0.1)O2 (NCM811)." "Investigation of Interface Reaction between LiCoO2 and Sulfide Electrolyte in an All-Solid-State Battery from First-Principle Structure Prediction Method","Investigation of Interface Reaction between LiCoO2 and Sulfide Electrolyte in an All-Solid-State Battery from First-Principle Structure Prediction Method","高 博, ハレム ランディ, Yamming Ma, 館山 佳尚","高 博, ハレム ランディ, Yamming Ma, 館山 佳尚","第59回電池討論会","第59回電池討論会","2018-11-27","","eng","oral_presentation","","","","",""," Solid-state lithium-ion batteries (SS-LIBs) is of great interest because of its high safety and high energy density in comparison to traditional liquid-electrolyte based batteries. However, there is a crucial issue about the interface resistance between the cathode and electrolyte in many SS-LIBs, which hinders the performance of batteries. To understand the microscopic mechanism of the interface resistance, we have been working on the DFT calculation analysis of the cathode – solid electrolyte interfaces with a systematic structure search. However, the explorations were still insufficient. Note that solid-solid interfaces seem more difficult than solid-liquid ones from a viewpoint of search for metastable structures. In this study, we utilized the CALYPSO structure prediction approach to investigate the interface configurations between LiCoO2 cathode and Li3PS4 sulfide solid electrolyte, and search the energetically stable and metastable structures. Several efficient techniques have been applied in our method, including an algorithm for searching lattice-matched superlattice, a structure generation method including the local coordination environment and the lattice shift between two materials. For the metastable structures successfully obtained, we calculated the electronic states and Li vacancy formation energies. We then found that there are interfacial Li sites where preferential Li depletion can occur upon charging, even in very disordered interfaces. This suggests that the Li-depleted layer mechanism plays a major role for the interfacial resistance. Besides, this study presents a new protocol of predicting the structures of solid-solid interface at the atomic scale. ","" "Dynamic behavior of magnesium deposition/dissolution in ROMgCl/Mg(TFSA)2/G3 electrolyte studied by in situ FT-IR technique","In situ FT-IR法を用いたROMgCl/Mg(TFSA)2/G3電解液の動的Mg析出溶解挙動の分析","万代俊彦, 宗健也, 袖山 慶太郎, 館山 佳尚, 金村聖志","万代俊彦, 宗健也, 袖山 慶太郎, 館山 佳尚, 金村聖志","第59回電池討論会","第59回電池討論会","2018-11-27","","jpn","oral_presentation","","","","","","","Magnesium secondary batteries are one of promising innovative batteries owing to their high energy density as well as the cost effectiveness and safety of the bulk Mg metal. Ethereal solutions of Mg(TFSA)2 combined with chloride compounds show excellent behavior for the Mg deposition/dissolution processes while poor those without chloride. In situ FT-IR spectra of the Mg(TFSA)2/ether electrolytes with/without chloride clearly demonstrated the change in mechanism especially for the deposition process." "電池界面イオニクスに関する第一原理統計サンプリング研究","電池界面イオニクスに関する第一原理統計サンプリング研究","館山 佳尚","館山 佳尚","2018年日本表面真空学会学術講演会","2018年日本表面真空学会学術講演会","2018-11-20","","jpn","oral_presentation","","","","","","","固液界面における化学反応・電気化学反応は電池・触媒の性能を左右する重要素過程であり、その理解と制御が基礎的にも応用的にも重要であることは論を俟ない。しかし、固液界面反応のその場観察・オペランド観察は、近年技術開発が著しく進んでいるものの、いまだに困難が多い。そのような状況において、“予言性の高い”理論計算研究による微視的機構提案のニーズは高い。 我々は、そのような理論計算研究の実践による、電池・触媒に関する本質的問題の解決に取り組んできた。その中で、酸化還元反応に対する密度汎関数理論(DFT)ベースの手法開発、DFTレベルの大規模系長時間サンプリングコードの開発、固液界面における化学反応自由エネルギー計算、バイアス効果の検討、界面構造サンプリングといったことを扱ってきた。本講演では特に蓄電池界面付近におけるイオンダイナミクス・反応を題材にしながら、上記の取り組みについて紹介する。" "ポストリチウムイオン電池に向けた電解質界面・被膜の物性解明と材料設計","ポストリチウムイオン電池に向けた電解質界面・被膜の物性解明と材料設計","館山 佳尚","館山 佳尚","第5回「京」を中核とするHPCIシステム利用研究課題成果報告会","第5回「京」を中核とするHPCIシステム利用研究課題成果報告会","2018-11-02","","jpn","oral_presentation","","","","","","","HPCI資源(京)を用いたポストリチウムイオン電池に向けた電解質界面・被膜の物性解明と材料設計について紹介する。" "炭素ダイヤモンド電極界面の触媒・化学反応に関する第一原理計算解析","炭素ダイヤモンド電極界面の触媒・化学反応に関する第一原理計算解析","濱田幾太郎, 館山 佳尚","濱田幾太郎, 館山 佳尚","第5回「京」を中核とするHPCIシステム利用研究課題成果報告会","第5回「京」を中核とするHPCIシステム利用研究課題成果報告会","2018-11-02","","jpn","oral_presentation","","","","","","","HPCI計算資源を用いた炭素ダイヤモンド電極界面の触媒・化学反応に関する第一原理計算解析について紹介する。" "Theoretical Study on Termination Dependent Redox Reactivity of Boron Doped Diamond / Water Interface","Theoretical Study on Termination Dependent Redox Reactivity of Boron Doped Diamond / Water Interface","飯塚 将太, 夏井敬介, 栄長泰明, 館山 佳尚","飯塚 将太, 夏井敬介, 栄長泰明, 館山 佳尚","14th International Conference on Atomically Controlled Surfaces, Interfaces and Nanostructures (ACSIN-14)","14th International Conference on Atomically Controlled Surfaces, Interfaces and Nanostructures (ACSIN-14)","2018-10-21","","eng","oral_presentation","","","","","","Boron doped diamond (BDD) electrode has several unusual characteristics for electrocatalysis and sensor applications. Recently, the cyclic voltammogram measurement showed that the redox reactivity of BDD significantly depends on the termination. To understand the mechanisms, we carried out density-functional theory based molecular dynamics studies on hydrogenated, oxidized and fluorinated BDD interfaces with bulk water. We then found that the interfacial band offset between BDD and water depends on the termination. If the band edge pinning regime holds, the results indicated that the space-charge layer plays a crucial role, partially with the electric double layer, for the charge transfer at the semiconductor / liquid interfaces under bias.","" "DFT Investigations of Surface Defects in Li(NixCoyMnz)O2 Layered Materials: Promising Cathode for Next Generation Battery","DFT Investigations of Surface Defects in Li(NixCoyMnz)O2 Layered Materials: Promising Cathode for Next Generation Battery","シュクリ ガネス, 館山 佳尚, ハレム ランディ","シュクリ ガネス, 館山 佳尚, ハレム ランディ","14th International Conference on Atomically Controlled Surfaces, Interfaces and Nanostructures (ACSIN-14)","14th International Conference on Atomically Controlled Surfaces, Interfaces and Nanostructures (ACSIN-14)","2018-10-21","","eng","oral_presentation","","","","","","Layered Ni-rich Li(NixMnyCoz)O2 (x≧0.5, x+y+z=1) or NCM is a promising candidate for the next-generation Li-ion battery cathodes because of its high energy density. However, there are still some critical issues; (1) NCM lattice oxygen release during operation, (2) capacity fading due to the irreversible layered to spinel/rock-salt phase transformation. In this work, by means of density functional theory (DFT)-based calculations, we investigated the oxygen vacancy (Ovac) formation and Ni/Li mixing defect formation at surface and near-surface regions of Li(Ni0.8Mn0.1Co0.1)O2 or NCM811 especially. Based on the energetics analysis, we found that the bulk and the three low-index surfaces considered in this work viz. (104), (110) and (012) are stable against spontaneous oxygen evolution in the fully lithiated state. On the other hand, there was a large variation of Ovac formation energy at the surfaces depending on the surface compositions of transition metals. We also observed similar tendency on the Ni/Li mixing defects. These results suggest an important insight to control the stability of the NCM cathodes.","" "蓄電池の技術課題に対する第一原理計算研究","蓄電池の技術課題に対する第一原理計算研究","館山 佳尚","館山 佳尚","PCoMSシンポジウム2018&計算物質科学スーパーコンピュータ共用事業報告会","PCoMSシンポジウム2018&計算物質科学スーパーコンピュータ共用事業報告会","2018-10-22","","jpn","oral_presentation","","","","","","","次世代蓄電池として全固体電池への注目が高まっている。近年の高イオン伝導度固体電解質の発見により、“電極—電解質界面”の安定性とイオン伝導性が最も重要な課題となってきた。この界面現象を明らかにするために様々な実験技術が開発されているが、電池動作下でのイオン・電子の動きについてまだ不明な点が多い。我々はこれらの問題を高精度理論計算を用いて解明しようと、研究を進めている。まず固固界面では、固液界面で用いられるような分子動力学計算だけは平衡構造到達が難しいこと、格子不整合が現象に効くことなどを考慮して、それらを解決する新たな計算技術を開発し、硫化物電解質—酸化物正極におけるLiイオンの欠乏層成長メカニズムを実証してきた[1,2] 。それらに関する最近の進展について紹介する。 本研究は、物質・材料研究機構Bo Gao博士、Randy Jalem博士、および現在東大物性研の春山潤博士との共同研究である。 " "第一原理計算と微視的反応速度論に基づく理論計算によるメタン酸化カップリングの活性と選択性の予測","第一原理計算と微視的反応速度論に基づく理論計算によるメタン酸化カップリングの活性と選択性の予測","石川 敦之, 館山 佳尚","石川 敦之, 館山 佳尚","第122回触媒討論会","第122回触媒討論会","2018-09-26","","jpn","oral_presentation","","","","","","","Oxidative coupling of methane (OCM), an important catalytic reaction in natural gas utilization, has been studied by theoretical approach. The OCM using Li-doped magnesia was examined here. The kinetic parameters such as activation energy or reaction energy was calculated by first principle density functional theory, and these are used in the further microkinetics and reactor simulations. We clarified that higher CH4 conversion can be achieved with the help of the Li doping, since O atom next to Li is effective in abstracting H atom from CH4. Also, the selectivity of C2 compounds against the total combustion pathway (CO and CO2 formation) will be discussed." "DFT Sampling Calculation Studies on Electrode / Electrolyte Interfaces in Li Ion Batteries","DFT Sampling Calculation Studies on Electrode / Electrolyte Interfaces in Li Ion Batteries","館山 佳尚","館山 佳尚","12th Japan-France Joint Seminar on Batteries","12th Japan-France Joint Seminar on Batteries","2018-09-19","","eng","oral_presentation","","","","","","There remain many long-standing issues on interfacial phenomena in batteries. Representative is structure and characteristics of solid electrolyte interphase (SEI) formed in the anode / electrolyte interface. Recently, role of the cathode electrolyte interphase (CEI) in the cathode side has attracted much attention as well. In the field of solid-state battery (SSB), the origin and the remedy of interfacial resistance, a most serious bottleneck, has been debated. Those interfacial phenomena are crucial for improving the performance and the reliability of the secondary batteries, whereas they have not been fully understood yet because of the difficulty in the in-situ measurements as well as accurate calculations.","" "第一原理計算•微視的反応論•反応工学に基づくメタン酸化カップリング活性と選択性の理論予測","第一原理計算•微視的反応論•反応工学に基づくメタン酸化カップリング活性と選択性の理論予測","石川 敦之, 館山 佳尚","石川 敦之, 館山 佳尚","第12回分子科学討論会","第12回分子科学討論会","2018-09-10","","jpn","oral_presentation","","","","","","","Oxidative coupling of methane (OCM), an important catalytic reaction in natural gas utilization, has been studied by theoretical approach. The OCM using Li-doped magnesia was examined here. The kinetic parameters such as activation energy or reaction energy was calculated by first principle density functional theory, and these are used in the further microkinetics and reactor simulations. We clarified that higher CH4 conversion can be achieved with the help of the Li doping, since O atom next to Li is effective in abstracting H atom from CH4. Also, the selectivity of C2 compounds against the total combustion pathway (CO and CO2 formation) will be discussed." "Mi2i蓄電池グループグループ紹介と最近の活動報告","Mi2i蓄電池グループグループ紹介と最近の活動報告","中山 将伸, 館山 佳尚, 袖山 慶太郎","中山 将伸, 館山 佳尚, 袖山 慶太郎","第7回MI2Iフォーラム","第7回MI2Iフォーラム","2018-09-12","","jpn","oral_presentation","","","","","","","Mi2i蓄電池グループグループ紹介と最近の活動報告" "Structure Search and Property Analysis of Interfaces between LiCoO2 Cathode and Sulfide Electrolyte in Solid-State Battery via DFT-CALYPSO Method","Structure Search and Property Analysis of Interfaces between LiCoO2 Cathode and Sulfide Electrolyte in Solid-State Battery via DFT-CALYPSO Method","高 博, ハレム ランディ, Yanming Ma, 館山 佳尚","高 博, ハレム ランディ, Yanming Ma, 館山 佳尚","International Workshop COMDI2018","International Workshop COMDI2018","2018-09-10","","jpn","oral_presentation","","","","","",""," Solid-state lithium-ion batteries (SS-LIBs) is of great interest because of its high safety and high energy density in comparison to traditional liquid electrolytes based batteries. However, there is a crucial issue about the interface resistance between the cathode and electrolyte in many SS-LIBs, which hinders the performance of batteries. To understand the microscopic mechanism of the interface resistance, we have been working on the DFT calculation analysis of the cathode – solid electrolyte interfaces with a systematic structure search. However, the explorations were still insufficient. Note that solid-solid interfaces seem more difficult than solid-liquid ones from a viewpoint of search for metastable structures. In this study, we utilized the CALYPSO structure prediction ap" "DFT-MD studies on processes at interfaces of organic electrolyte, SEI film and graphite anode","DFT-MD studies on processes at interfaces of organic electrolyte, SEI film and graphite anode","館山 佳尚, 袖山 慶太郎","館山 佳尚, 袖山 慶太郎","69th Annual Meeting of the International Society of Electrochemistry","69th Annual Meeting of the International Society of Electrochemistry","2018-09-02","","eng","oral_presentation","","","","","","In this paper, we introduce our recent computational works on the possible formation mechanism of organic SEI film between graphite anode and ethylene carbonate (EC) electrolyte and Li+ ion transport between graphite anode and Li2CO3 SEI film. Most of the calculations were DFT-MD samplings at room temperature with PBE exchange correlation functional. Note that we carried out multiple runs with different initial configurations to obtain reasonably stable structures. ","" "DFT Study on CO2 Reduction on Boron-doped diamond Electrode","DFT Study on CO2 Reduction on Boron-doped diamond Electrode","館山 佳尚, 豆 茂峰, 飯塚 将太, 栄長泰明","館山 佳尚, 豆 茂峰, 飯塚 将太, 栄長泰明","69th Annual Meeting of the International Society of Electrochemistry","69th Annual Meeting of the International Society of Electrochemistry","2018-09-02","","eng","oral_presentation","","","","","","Boron-doped diamond (BDD) has attracted much attention due to its unique properties, like wide-potential window, low background current, high stability, and high selectivities, compared to the other electrodes. Recently, Nakata et al. demonstrated that electrochemical CO2 reduction generates more carbon hydrates instead of CO on the BDD electrode.1 In this work, we examined the mechanisms of this CO2 reduction on BDD with typical (111) interfaces with H- and OH-terminations, by means of density functional theory (DFT) calculations. The structures of considered products, like CO, HCOOH, and HCHO, as well as several radical species, like COOH*, HCOO* and CHO*, at the interfaces of water and BDD were investigated using DFT-based molecular dynamics. The pair radial distribution functions show that both possible products and radical species weakly interact with BDD interfaces. To further explore reaction paths, the reaction enthalpies were evaluated using computational hydrogen electrode approach.2 We found that hydrogenation of CO2 into HCOO* is energetically favorable than protonation of CO2* into COOH* on both (111)H and (111)OH surfaces (Figure 1). Moreover, H of HCOOH is lower than that of CO on both (111)H (H = 0.05 and 0.76 eV for HCOOH* and CO*, respectively) and (111)OH (H = 0.11 and 0.76 eV for HCOOH and CO, respectively) surfaces, which indicates formation of HCOOH* is energetically favorable than formation CO. In addition, further reduction of HCOOH* into HCHO* requires passing the radical special CHO* with high H (1.84 and 1.79 eV on (111)H and (111)OH surfaces, respectively). The mechanism of formation of HCOOH was further studied from in combination of the analysis of the electronic states.","" "Molecular dynamics simulation of water dynamics at the water/solid interface of ceria-supported Pt clusters","Molecular dynamics simulation of water dynamics at the water/solid interface of ceria-supported Pt clusters","サボバ ルチエ, Farnesi Camellone Matteo, Negreiros Ribeiro Fabio, 館山 佳尚, Fabris Stefano","サボバ ルチエ, Farnesi Camellone Matteo, Negreiros Ribeiro Fabio, 館山 佳尚, Fabris Stefano","TOCAT8 (The 8th Tokyo Conference on Advanced Catalytic Science a","TOCAT8 (The 8th Tokyo Conference on Advanced Catalytic Science a","2018-08-05","","jpn","oral_presentation","","","","","","","The present work is a theoretical analysis based on density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations investigating the physical and chemical properties of H2O/Pt6/CeO2 material. Water-ceria interface exhibits increased H2O dissociation and partial surface hydroxylation of the CeO2 surface. The hydroxylated surface allows for fast proton diffusion along the water-ceria interface which promotes a transfer of OH molecules towards adsorbed Pt nanoparticle. The presence of water solvent induces charge reorganization at the Pt-ceria material creating new active centers for OH adsorption." "NO + CO Reaction on Rh Surface: First Principle Density Functional Theory Investigation Combined with Microkinetic Analysis","NO + CO Reaction on Rh Surface: First Principle Density Functional Theory Investigation Combined with Microkinetic Analysis","石川 敦之, 館山 佳尚","石川 敦之, 館山 佳尚","Pre-conference of TOCAT8 and 5th International Symposium of ICAT","Pre-conference of TOCAT8 and 5th International Symposium of ICAT","2018-08-03","","jpn","oral_presentation","","","","","","","In this study, the NO + CO reaction on Rh surface is studied, as this reaction is widely used as a model reaction on the NOx reduction by the three-way catalyst. Density functional theory (DFT) calculation combined with microkinetic analysis was used. We assumed that the catalysis cycle consists of the following elementary reaction steps; NO dissociation, N2O formation, N2 formation, and CO2 formation. Here, the adsorption energies, reaction energies, and activation energies were all evaluated with the DFT calculations." "Reversible O redox in Layered Hexagonal Transition Metal Oxides for Na Ion Battery Cathodes with High Potential and High Capacity","Reversible O redox in Layered Hexagonal Transition Metal Oxides for Na Ion Battery Cathodes with High Potential and High Capacity","大久保將史, 山田淳夫, 館山 佳尚","大久保將史, 山田淳夫, 館山 佳尚","ACEMD18, Australian Computationally enhanced Materials Design 18","ACEMD18, Australian Computationally enhanced Materials Design 18","2018-07-22","","jpn","oral_presentation","","","","","","","Increasing the capacity of Na ions batteries is a highly desired industrial goal. One possible way of achieving such an increase is evoking reversible oxygen redox that would add extra capacity to that of transition metal (TM) redox. To understand the atomistic origin of the O redox, we carried out a comprehensive density functional study of the electronic properties of the R-3m Na2RuO3 (space group 166) and R-3 Na1RuO3 (space group 148) as shown in Figure 1. It was speculated that these compounds undergo reversible O redox which increases the capacity by 40% beyond the TM redox capacity to an impressive value of 180 mA.h/g. We then screened the full range of ternary R3 ̅ compounds that consist of Na, O and 4d transition metal (TM) elements in search for candidate compositions with hi" "Grignard Reagent Based Electrolytes in Magnesium-Ion Battery : A First-Principles Study","Grignard Reagent Based Electrolytes in Magnesium-Ion Battery : A First-Principles Study","チョーダリー アシュ, 袖山 慶太郎, 館山 佳尚","チョーダリー アシュ, 袖山 慶太郎, 館山 佳尚","19th International Meeting on Lithium Batteries","19th International Meeting on Lithium Batteries","2018-06-17","","jpn","oral_presentation","","","","","","","Magnesium-ion batteries (MIBs) have gained considerable attention as an alternative energy storage to Li-ion batteries in the past few decades [1,2]. Grignard reagent (R-Mg-X: X=halogen) with ether has been one of the most studied and efficient solutions for MIB. However, the microscopic behaviours in the electrolyte solution are still under debate. To gain insight of the solvation on the atomic scale, we performed the first-principle molecular dynamics samplings of such MIB electrolytes using the CPMD code. The study was also motivated for understanding the fundamental mechanisms of electrolytes for 2+ cation and the underlying differences instead of 1+ cation. We carried CPMD simulations of a single R-Mg-X (where R=Methyl, Ethyl and Phenyl) in different cubic boxes with 44 tetrahydrofura" "Surveying Ilmenite Type 4d Transition Metal Oxides for Na Ion Battery Cathodes with High Potential and High Capacity","Surveying Ilmenite Type 4d Transition Metal Oxides for Na Ion Battery Cathodes with High Potential and High Capacity","アルアサディ フセインナシーフモハマド, 大久保將史, 山田淳夫, 館山 佳尚","アルアサディ フセインナシーフモハマド, 大久保將史, 山田淳夫, 館山 佳尚","IMLB 2018 - The 19th International Meeting on Lithium Batteries","IMLB 2018 - The 19th International Meeting on Lithium Batteries","2018-06-17","","jpn","oral_presentation","","","","","","","We present a comprehensive density functional study screening the full range of ternary hexagonal layered compounds of ilmenite type structure (space group 148, R-3) that consist of Na, O and 4d transition metal (TM) elements in search for candidates with high potential and large capacity for sodium ion battery cathodes.Computationally, we treated the exchange correlation functional with GGA+U formalism. U term was particularly fine-tuned to reproduce the electrochemical potential of Na extraction in NaxRuO3 compound for which measurements exist. We found that U = 2 eV fulfils this criterion and moreover it produces an electronic structre that resembles the one obtained with higher level HSE03 functional." "First-Principles Study on Adsorption and Decomposition of Carbonate Electrolyte Molecules at LiNi0.5Mn1.5O4 Cathode Interface","First-Principles Study on Adsorption and Decomposition of Carbonate Electrolyte Molecules at LiNi0.5Mn1.5O4 Cathode Interface","館山 佳尚, 奥野幸洋, 後瀉敬介, 袖山 慶太郎","館山 佳尚, 奥野幸洋, 後瀉敬介, 袖山 慶太郎","19th International Meeting on Lithium Batteries (IMLB2018)","19th International Meeting on Lithium Batteries (IMLB2018)","2018-06-17","","eng","oral_presentation","","","","","","Electrolyte decomposition on the cathode surfaces of lithium-ion batteries has attracted considerable attention because it leads to battery degradation and formation of cathode solid-electrolyte interphase (CEI). [1] In this study, we used density functional theory (DFT) calculations to investigate the adsorption distribution of ethylene carbonate (EC) electrolyte molecules as well as EC decomposition reactions on the (100) surfaces of lithiated (pristine) and de-lithiated forms of spinel-type LiNi0.5Mn1.5O4 (LNMO) as model cathode surfaces.","" "Interfacial ionics and electronics in battery and catalyst","Interfacial ionics and electronics in battery and catalyst","館山 佳尚","館山 佳尚","Workshop ""Simulations in Physical cheistRy: an International Kermesse in Paris""","Workshop ""Simulations in Physical cheistRy: an International Kermesse in Paris""","2018-05-28","","eng","oral_presentation","","","","","","In this talk, I will introduce our recent works; (i) Li depletion behaviour at sulfide electrolyte – oxide cathode interfaces upon charging in “solid-state” Li-ion battery, a promising next-generation battery [1,2], (ii) Free energy profile of Li-ion transport between graphite anode and inorganic solid electrolyte interphase (SEI) film upon charging and discharge, a long-standing issue in Li-ion battery [3], (iii) Catalytic redox reaction reactivity of boron-doped diamond electrodes with extraordinary potential window, depending on the surface terminations [4]. Along with these studies, I discuss the bias effect as well.","" "DFT+U and molecular dynamics study of H2O interaction with metal/ceria materials","DFT+U and molecular dynamics study of H2O interaction with metal/ceria materials","サボバ ルチエ, Matteo Farnesi Camellone, Fabio Negreiros Ribeiro, 館山 佳尚, Vladimir Matolin, Stefano Fabris","サボバ ルチエ, Matteo Farnesi Camellone, Fabio Negreiros Ribeiro, 館山 佳尚, Vladimir Matolin, Stefano Fabris","JCS’18 (7th JCS Symposium, Prague)","JCS’18 (7th JCS Symposium, Prague)","2018-05-21","","jpn","oral_presentation","","","","","","","Ceria-based materials have important applications in heterogeneous catalysis as well as for renewable energy technologies such as fuel cells. In this work we study the properties of ceria-supported Pt6 nanoparticle in water solution by the means of DFT+U and ab initio molecular dynamics calculations. We analyze the structure of the interfacial water layer and its effect on the structure and charge of the Pt nanoparticle. We show that the Grotthus-like mechanism for H/OH transfer along ceria surface observed on H2O/CeO2 interface allows for faster transport of OH molecules towards the active sites on the Pt cluster. The presence of water solvent induces charge reorganization at Pt-ceria material unlocking new stable active centers available for water adsorption/dissociation as well as promo" "NO + CO Reaction on Rh Surface: DFT Investigation Combined with Microkinetic Analysis","NO + CO Reaction on Rh Surface: DFT Investigation Combined with Microkinetic Analysis","石川 敦之, 館山 佳尚","石川 敦之, 館山 佳尚","The 7th JCS (Japan-Czech-Slovak) Symposium","The 7th JCS (Japan-Czech-Slovak) Symposium","2018-05-21","","jpn","oral_presentation","","","","","","","In this study, the NO + CO reaction on Rh surface is studied, as this reaction is widely used as a model reaction on the NOx reduction by the three-way catalyst. Density functional theory (DFT) calculation combined with microkinetic analysis was used. We assumed that the catalysis cycle consists of the following elementary reaction steps; NO dissociation, N2O formation, N2 formation, and CO2 formation." "First-Principles Study on the Microscopic Origin of Interfacial Resistance between Oxide Cathode and Sulfide Electrolyte in All Solid State Battery","First-Principles Study on the Microscopic Origin of Interfacial Resistance between Oxide Cathode and Sulfide Electrolyte in All Solid State Battery","館山 佳尚, 春山潤, 袖山 慶太郎","館山 佳尚, 春山潤, 袖山 慶太郎","2018 MRS Spring Meeting & Exhibit","2018 MRS Spring Meeting & Exhibit","2018-04-02","","jpn","oral_presentation","","","","","","","We have investigated those properties such as potential origins of the interfacial resistance (e.g. space-charge layer model, reaction layer model) as well as the buffer layer effect by using first-principles DFT+U calculations [2.3]. As a representative model system, LiCoO2 (LCO), β-Li3PS4 (LPS), and LiNbO3 (LNO) were selected for cathode, sulfide electrolyte, and buffer layer, respectively. We carried out first-principles calculations of the several possible interface configurations and obtained the stable structures and the electronic states. Besides, we calculated the sitedependent Li chemical potentials with respect to Li metal. The results indicate that the Li depletion can proceed at the beginning of the charge process, which may correspond to the space-charge layer scenario, and t" "Combining Materials Modelling and Informatics Techniques for Efficient Search of Fast Lithium Ionic Conductors for All-Solid-State Battery Application","Combining Materials Modelling and Informatics Techniques for Efficient Search of Fast Lithium Ionic Conductors for All-Solid-State Battery Application","ハレム ランディ, 館山 佳尚, 中山 将伸","ハレム ランディ, 館山 佳尚, 中山 将伸","International Battery Seminar and Exhibit","International Battery Seminar and Exhibit","2018-03-26","","jpn","oral_presentation","","","","","","","In here, we present our recent efforts aimed towards the development of an effective and efficient search/screening workflow for fast lithium ionic conductors. We highlight our developed general representation schemes (accounting for cell periodicity, atom ordering, and number of atoms) for inorganic compounds or crystalline solids, demonstrating their predictive power for various DFT-calculated material properties such as cohesive energy, material density, electronic band gap energy, and thermodynamic decomposition energy. We also present our informatics-aided DFT-based screening of a chemical search space with olivine- and tavorite-type structures and with ion migration energy and thermodynamic stability as criteria." "DFT-MD study on highly salt-concentrated electrolytes: A new class of battery electrolytes","DFT-MD study on highly salt-concentrated electrolytes: A new class of battery electrolytes","館山 佳尚","館山 佳尚","CECAM Workshop “Electrostatics in Concentrated Electrolytes”","CECAM Workshop “Electrostatics in Concentrated Electrolytes”","2018-03-20","","jpn","oral_presentation","","","","","","","We investigated the mechanism of unusual electrochemical stability and ion diffusion of Li-TFSA and Li-FSA salts in AN solvents by using DFT-MD sampling. TFSA anion sacrificially accepts a reductive electron and dissociates the CF3 moiety, instead of AN solvents. AN decomposition, observed experimentally, dose not proceed by 1e reduction but 2e reduction is required. Ion diffusion calculations of LiTFSA and LiFSA indicate that, in HC conditions, the Stokes’ Law doesn’t seem to hold, and the transport number of Li increases. This suggests that there are non-conventional Li+ diffusion mechanisms in HC condition." "Revisiting Grignard reagent based electrolytes in magnesium-ion battery : a first-principles study","Revisiting Grignard reagent based electrolytes in magnesium-ion battery : a first-principles study","チョーダリー アシュ, 袖山 慶太郎, 館山 佳尚","チョーダリー アシュ, 袖山 慶太郎, 館山 佳尚","International Battery Association 2018","International Battery Association 2018","2018-03-11","","jpn","oral_presentation","","","","","","","Magnesium-ion batteries (MIBs) have gained considerable attention as an alternative energy storage to Li-ion batteries in the past few decades [1,2]. Grignard reagent (R-Mg-X: X=halogen) with ether has been one of the most studied and efficient solutions for MIB. However, the microscopic behaviours in the electrolyte solution are still under debate. To gain insight of the solvation on the atomic scale, we performed the first-principle molecular dynamics samplings of such MIB electrolytes using the CPMD code. The study was also motivated for understanding the fundamental mechanisms of electrolytes for 2+ cation and the underlying differences instead of 1+ cation. We carried CPMD simulations of a single R-Mg-X (where R=Methyl, Ethyl and Phenyl) in different cubic boxes with 44 tetrahydrofura" "Computational Study on Electrolytes based on Grignard Reagents for Magnesium-Ion Battery","Computational Study on Electrolytes based on Grignard Reagents for Magnesium-Ion Battery","チョーダリー アシュ, 袖山 慶太郎, 館山 佳尚","チョーダリー アシュ, 袖山 慶太郎, 館山 佳尚","ポスト「京」重点課題5 第4回公開シンポジウム","ポスト「京」重点課題5 第4回公開シンポジウム","2017-12-11","","jpn","oral_presentation","","","","","","","Magnesium-ion batteries (MIBs) have gained considerable attention as an alternative energy storage to Li-ion batteries in the past few decades [1,2]. Grignard reagent (R-Mg-X: X=halogen) with ether has been one of the most studied and efficient solutions for MIB. However, the microscopic behaviours in the electrolyte solution are still under debate. To gain insight of the solvation on the atomic scale, we performed the first-principle molecular dynamics samplings of such MIB electrolytes using the CPMD code. The study was also motivated for understanding the fundamental mechanisms of electrolytes for 2+ cation and the underlying differences instead of 1+ cation. The compatibility of electrolyte for reversible dissolution/deposition of Mg2+ is the most important factor to determine Coulomb" "有機電解液系に向けたDFT-MDに対するvdw相互作用の検証","有機電解液系に向けたDFT-MDに対するvdw相互作用の検証","飯塚 将太, 館山 佳尚","飯塚 将太, 館山 佳尚","ポスト「京」重点課題5 第4回公開シンポジウム","ポスト「京」重点課題5 第4回公開シンポジウム","2017-12-11","","jpn","oral_presentation","","","","","","","2次電池や太陽電池といったエネルギーを変換、貯蔵する系の電解液には、しばしば有機液体が用いられる。放電、充電といった有機分子の反応のメカニズムを理解するには、原子スケールの分子動力学計算が欠かせない。同時に、有機電解液系では、van der Waals (vdW)相互作用が非常に重要な役割を果たすので、密度汎関数理論における標準的な交換-相関汎関数であるPBEを用いた第一原理分子動力学法においても、vdW相互作用を考慮する必要がある。第一原理分子動力学ソフトウェアstat-CPMDには、DFT-D2の枠組みを用いてvdW相互作用を考慮した計算が可能だが、新たに精度の高いDFT-D3を導入した。まず、固体アルゴンやベンゼンダイマーなど、基礎的な固体、分子について、分子間距離や固体密度の計算を行い、DFT-D3を含めたエネルギーや、原子にかかる力が正しく計算されていることを確認した。また、水、および代表的な有機溶媒であるエチレンカーボネート(EC)とプ" "DFT molecular dynamics sampling studies on battery phenomena and materials on the atomic scale","DFT molecular dynamics sampling studies on battery phenomena and materials on the atomic scale","館山 佳尚","館山 佳尚","4th International Conference on Advanced Electromaterials","4th International Conference on Advanced Electromaterials","2017-11-21","","jpn","oral_presentation","","","","","","","Search for batteries with better performance (larger energy density) and more reliability (more safety) has been extensively carried out for decades. However, the atomistic mechanisms of chemical (redox) reactions and ion transports in batteries have not been fully understood yet, because of the difficulty in the in-situ measurements. A long-standing issue is SEI (solid electrolyte interphase) properties and its formation mechanism at negative electrode – organic electrolyte interface at the first charging, which really determines the performance and reliability of the battery. Recently, a novel concept of superconcentrated liquid electrolyte has been proposed and attracted much attention as promising future electrolytes." "Mg3Bi2合金負極の表面および欠陥に関する第一原理計算解析","Mg3Bi2合金負極の表面および欠陥に関する第一原理計算解析","カークム ジェームス クリストファー, 濱田 幾太郎, 桑田紘子, 松井雅樹, 館山 佳尚","カークム ジェームス クリストファー, 濱田 幾太郎, 桑田紘子, 松井雅樹, 館山 佳尚","第58回電池討論会","第58回電池討論会","2017-11-14","","jpn","oral_presentation","","","","","","","ポストLiイオン電池の一つとしてMgイオン電池(MIB)が注目を集めている。金属負極を考える場合、Liイオン電池(LIB)に匹敵する体積エネルギー密度を原理的に有し、またデンドライト形成がされないことから、性能面、安全面で利点が存在する。一方、このMg金属負極は不動態膜に容易に覆われ、Mgイオンの高効率な溶解・析出が実際にはかなり難しいという問題がある。このMg金属の代替負極として、筆者の一部がMg3Bi2合金の利用可能性を提案している1。このMg3Bi2は適当な条件を選ぶと安定した溶解・析出挙動を示す。しかしながら、その微視的機構ついてはまだよくわかっておらず、溶解・析出挙動の基礎的理解もままならない。本研究では特に表面および表面近傍の欠陥に着目した包括的な第一原理計算解析を実行し、Mg3Bi2負極におけるMgイオンの挿入・脱離について考察を行った2" "層状化合物NaxMO3 (M=4d遷移金属)の酸素レドックスに関する理論計算研究","層状化合物NaxMO3 (M=4d遷移金属)の酸素レドックスに関する理論計算研究","アルアサディ フセインナシーフモハマド, 大久保將史, 山田淳夫, 館山 佳尚","アルアサディ フセインナシーフモハマド, 大久保將史, 山田淳夫, 館山 佳尚","第58回電池討論会","第58回電池討論会","2017-11-14","","jpn","oral_presentation","","","","","","","ナトリウムイオン電池は、構成元素の資源的優位性のみならず、リチウムイオン電池と類似した動作機構を持つこと、高速イオン伝導が期待されることなどから、ポストリチウムイオン電池の一つして注目を集めている。しかし、リチウムイオン電池に匹敵する高電圧・高容量を得ることが難しく、エネルギー密度が十分に確保できないことが実用化を阻む要因の一つとなっている。問題解決に向け、現在様々な正極・負極の開発が行われており、筆者らは酸化物イオンのレドックス反応による安定な付加容量を示すNa過剰正極Na2-xRuO3 (x=0-1.5)を見出した1。本材料は充放電中に構造崩壊を一切起こさないためモデル系として最適であり、第一原理計算を用いて酸化物イオンが寄与する付加容量の起源を明らかにした上で、他の4d遷移金属酸化物を基本とする新規高容量正極材料の探索を試みた2。" "ポストリチウムイオン電池開発に向けた電解質界面被膜の物性解明と材料設計","ポストリチウムイオン電池開発に向けた電解質界面被膜の物性解明と材料設計","館山 佳尚","館山 佳尚","第4回「京」を中核とするHPCIシステム利用研究課題 成果報告会","第4回「京」を中核とするHPCIシステム利用研究課題 成果報告会","2017-11-02","","jpn","oral_presentation","","","","","","","The multivalent ions and electrolytes interaction affect ion transport kinetics and deposition/dissolution processes.The THFs in the solvation shell of Mg2+ shows the attractive interactions which causes the frequencies of C-O to be Red shifted as compared to the bulk THFs." "第一原理計算を用いたリチウムイオン電池正極/固体電解質界面の研究","第一原理計算を用いたリチウムイオン電池正極/固体電解質界面の研究","木野 日織, 館山 佳尚","木野 日織, 館山 佳尚","第4回「京」を中核とするHPCIシステム利用研究課題 成果報告会","第4回「京」を中核とするHPCIシステム利用研究課題 成果報告会","2017-11-02","","jpn","oral_presentation","","","","","","","All-solid-state Li-ion batteries (ASS-LIBs) are one of the promising next-generation batteries because of their large energy density and high stability. However, when the sulfide electrolytes are used for ASS-LIBs, huge resistance is observed at oxide cathode/sulfide electrolyte interface. Buffer layer coating considerably decreases the interfacial resistance.1,2 We have explored the origin of these behaviours by first-principles calculations with some techniques." "炭素ダイヤモンド電極触媒界面の触媒反応に関する第一原理計算解析","炭素ダイヤモンド電極触媒界面の触媒反応に関する第一原理計算解析","濱田 幾太郎, 館山 佳尚","濱田 幾太郎, 館山 佳尚","第4回「京」を中核とするHPCIシステム利用研究課題 成果報告会","第4回「京」を中核とするHPCIシステム利用研究課題 成果報告会","2017-11-02","","jpn","oral_presentation","","","","","","","We have investigated CO2 reduction mechanism at typical BDD(111) interfaces with different types of terminations, namely, H-, OH-, and (H,OH)-mixed terminations, by using first-principles density functional theory calculations. We found that neither H- nor OH-terminated surface is active for CO2 reduction. The surfaces with (OH,H)-mixed terminations, however, are found active for CO2 reduction towards HCOOH, where the isolated -OH termination decreases the energy of HCOO*. Moreover, involvement of the dimer –OH termination in the reaction opens a different pathway towards formation of HCHO." "Solid-Liquid and Solid-Solid Interfaces in Batteries and Catalysts: Computational Explorations","Solid-Liquid and Solid-Solid Interfaces in Batteries and Catalysts: Computational Explorations","館山 佳尚","館山 佳尚","8th International Symposium on Surface Science (ISSS-8)","8th International Symposium on Surface Science (ISSS-8)","2017-10-23","","jpn","oral_presentation","","","","","","","To elucidate these issues from the theoretical and computational sides, we have developed highly-efficient DFT-based sampling (free energy calculation) code, stat-CPMD, for supercomputers such as the K computer. Then, we have addressed (1) the formation mechanisms and the structural characters of SEI films at Li-intercalated graphite anode / EC-based organic electrolyte [1-3], and (2) investigated effects of the space-charge layer as well as the reaction layer on the interface states between the cathode and the sulfide solid electrolyte in ASSBs [4,5]." "Termination effects on CO2 Reduction at Borondoped Diamond electrodes: Ab-initio Study","Termination effects on CO2 Reduction at Borondoped Diamond electrodes: Ab-initio Study","豆 茂峰, 飯塚 将太, 栄長泰明, 館山 佳尚","豆 茂峰, 飯塚 将太, 栄長泰明, 館山 佳尚","Car-Parrinello Molecular Dynamics in 2017","Car-Parrinello Molecular Dynamics in 2017","2017-10-18","","jpn","oral_presentation","","","","","","","Boron-doped diamond (BDD) exhibits unique CO2 reduction behaviors such as major production of formic acid (HCOOH) and formaldehyde (HCHO), in contrast to the other metal surfaces where CO is often produced. To understand the microscopic origin, we have investigated the CO2 reduction mechanism at typical BDD (111) interfaces with different types of terminations, involving H-, OH-, and (H,OH)-mixed terminations, by using density functional theory (DFT) calculations. The structures of different intermediates at the interfaces of water and BDD were investigated using DFT-based molecular dynamics. The pair radial distribution functions show that the key intermediates weakly interact with BDD interfaces." "Oxygen Contribution to Redox Ilmenite Type 4d Transition Metal Oxide; Applications in Na ion Batteries","Oxygen Contribution to Redox Ilmenite Type 4d Transition Metal Oxide; Applications in Na ion Batteries","アルアサディ フセインナシーフモハマド, 館山 佳尚","アルアサディ フセインナシーフモハマド, 館山 佳尚","Car-Parrinello Molecular Dynamics in 2017 (CPMD2017)","Car-Parrinello Molecular Dynamics in 2017 (CPMD2017)","2017-10-18","","jpn","oral_presentation","","","","","","","We aimed at finding high capacity Na ion cathodes by examining allmechanisms that increase the capacity beyond that of transition metal redox.Using DFT, we screened the full range of hexagonal layered compounds withNaxTMO3 formula. We found that O" "DFT-D3 implementation in CPMD program for investigation of organic electrolyte solution","DFT-D3 implementation in CPMD program for investigation of organic electrolyte solution","飯塚 将太, 館山 佳尚","飯塚 将太, 館山 佳尚","Car-Parrinello Molecular Dynamics in 2017","Car-Parrinello Molecular Dynamics in 2017","2017-10-18","","jpn","oral_presentation","","","","","","","Energy and environmental systems such as batteries and solar cells often use non-aqueous organic liquid in their electrolyte solutions. In doing atomistic simulations of such organic systems, van der Waals (vdW) interaction plays a crucial role. At the moment, the open CPMD program includes an option of DFT-D2 framework only. For possible increase of the vdW interaction accuracy as well as a variety of choices, we implemented DFT-D3 framework, seemingly more accurate than the DFT-D2, in the CPMD program and carried out the benchmark with the optimized/equilibrium structures of graphite, Ar dimer, liquid water and liquid ethylene carbonate (EC), a typical battery electrolyte.We then confirmed that PBE-D2 and PBE-D3 improve the structures of graphite and Ar dimer. In particular, the PBE-D3 " "Molecular dynamics simulation of water dynamics at the water/solidinterface of ceria-supported Pt clusters","Molecular dynamics simulation of water dynamics at the water/solidinterface of ceria-supported Pt clusters","サボバ ルチエ, Matteo Farnesi Camellone, Fabio Negreiros Ribeiro, 館山 佳尚, Stefano Fabris","サボバ ルチエ, Matteo Farnesi Camellone, Fabio Negreiros Ribeiro, 館山 佳尚, Stefano Fabris","Car-Parrinello Molecular Dynamics in 2017 ","Car-Parrinello Molecular Dynamics in 2017 ","2017-10-18","","jpn","oral_presentation","","","","","","","The present work is a theoretical analysis based on density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations investigating the physical and chemical properties of H2O/Pt6/CeO2 material.Water-ceria interface exhibits increased H2O dissociation and surface hydroxylation until equilibrium concentration of surface OH groups is reached. The hydroxylated surface allows for fast proton diffusion along the water-ceria interface similar to the Grotthus mechanism. This effectively promotes a transfer of OH molecules towards adsorbed Pt nanoparticle, resulting in adsorption structures different from those in gas phase. We show that presence of water solvent induces charge reorganization at Pt-ceria material unlocking new stable active centers available for water adsorption" "Ab Initio Study on Adsorption Structure and Decomposition Reactions of Electrolytes on the LiNi0.5Mn1.5O4","Ab Initio Study on Adsorption Structure and Decomposition Reactions of Electrolytes on the LiNi0.5Mn1.5O4","奥野 幸洋, 後瀉 敬介, 袖山 慶太郎, 館山 佳尚","奥野 幸洋, 後瀉 敬介, 袖山 慶太郎, 館山 佳尚","Car-Parrinello Molecular Dynamics in 2017 (CPMD2017)","Car-Parrinello Molecular Dynamics in 2017 (CPMD2017)","2017-10-18","","jpn","oral_presentation","","","","","","","Electrolyte decomposition on the “cathode” surfaces in Li-ion batterieshave recently attracted much attention from a viewpoint of batterydegradation and cathode solid electrolyte interphase (SEI or CEI). Adoptingthe lithiated and delithiated spinel-type LiNi0.5Mn1.5O4 (LNMO) cathodes asmodel systems, we have investigated the adsorption configurationdistribution of ethylene carbonate (EC) electrolyte as well as the ECdecomposition reactions on the LNMO (100) surface, by using densityfunctional theory (DFT) calculations. DFT molecular dynamics simulationsindicate that the EC solvent molecules have some characteristicorientations for the adsorption, which is in good agreement with theexperimental observations. Such multiple adsorption manners give rise toseveral EC decomposition " "Car-Parrinello Molecular Dynamics (CPMD) Study on Electrolytes based on Grignard Reagents for Magnesium-Ion Battery","Car-Parrinello Molecular Dynamics (CPMD) Study on Electrolytes based on Grignard Reagents for Magnesium-Ion Battery","チョーダリー アシュ, 袖山 慶太郎, 館山 佳尚","チョーダリー アシュ, 袖山 慶太郎, 館山 佳尚","Car-Parrinello Molecular Dynamics in 2017","Car-Parrinello Molecular Dynamics in 2017","2017-10-18","","jpn","oral_presentation","","","","","","","Magnesium-ion batteries (MIBs) have gained considerable attention as an alternative energy storage to Li-ion batteries in the past few decades [1,2]. Grignard reagent (R-Mg-X: X=halogen) with ether has been one of the most studied and efficient solutions for MIB. However, the microscopic behaviours in the electrolyte solution are still under debate. To gain insight of the solvation on the atomic scale, we performed the first-principle molecular dynamics samplings of such MIB electrolytes using the CPMD code. The study was also motivated for understanding the fundamental mechanisms of electrolytes for 2+ cation and the underlying differences instead of 1+ cation. The compatibility of electrolyte for reversible dissolution/deposition of Mg2+ is the most important factor to determine Coulomb" "NO + CO Reaction on Rh Surface: DFT Investigation Combined with Microkinetic Analysis","NO + CO Reaction on Rh Surface: DFT Investigation Combined with Microkinetic Analysis","石川 敦之, 袖山 慶太郎, 館山 佳尚","石川 敦之, 袖山 慶太郎, 館山 佳尚","Car-Parrinello Molecular Dynamics in 2017","Car-Parrinello Molecular Dynamics in 2017","2017-10-18","","jpn","oral_presentation","","","","","","","This study investigates the NO + CO reaction on Rh surface, which is widely used to model the NOx reduction by three-way catalyst in gasoline-fueled automobiles. The catalytic cycle of this reaction consists of the following elementary steps: NO dissociation, N2O formation, N2 formation and CO2 formation. In this study, all these reactions were considered with the plane-wave density functional theory (DFT). Calculated adsorption, reaction, and activation energies were employed for the microkinetic analysis. N2O and N2 were found to be mainly formed at low and high temperatures, respectively, as known from previous experiments. This study shows that microkinetic analysis should be performed fully understand the temperature dependent catalytic reactivity." "DFT molecular dynamics studies on battery materials - SEI film and superconcentrated electrolyte","DFT molecular dynamics studies on battery materials - SEI film and superconcentrated electrolyte","館山 佳尚","館山 佳尚","6th Polish Forum Smart Energy Conversion & Storage","6th Polish Forum Smart Energy Conversion & Storage","2017-09-03","","jpn","oral_presentation","","","","","","","There remain many long-standing issues on interfacial phenomena in batteries. Representative is structure and characteristics of solid electrolyte interphase (SEI) formed in the anode / electrolyte interface. Recently, role of the cathode electrolyte interphase (CEI) in the cathode side has attracted much attention as well. In the field of all-solid-state battery (ASSB), the origin and the remedy of interfacial resistance, a most serious bottleneck, has been debated. Those interfacial phenomena are crucial for improving the performance and the reliability of the secondary batteries, whereas they have not been fully understood yet because of the difficulty in the in-situ measurements as well as accurate calculations." "DFT sampling calculation studies on interfacial phenomena in Li-ion batteries","DFT sampling calculation studies on interfacial phenomena in Li-ion batteries","館山 佳尚","館山 佳尚","IUMRS-ICAM2017","IUMRS-ICAM2017","2017-08-28","","jpn","oral_presentation","","","","","","","There remain many long-standing issues on interfacial phenomena in the secondary batteries. A representative issue is structure and characteristics of solid electrolyte interphase (SEI) formed in the anode / electrolyte interface. Recently, role of the cathode electrolyte interphase (CEI) in the cathode side has attracted much attention as well. In the field of all-solid-state battery (ASSB), the origin and the remedy of interfacial resistance, a most serious bottleneck, has been debated. Those interfacial phenomena are crucial for improving the performance and the reliability of the secondary batteries, whereas they have not been fully understood yet because of the difficulty in the in-situ measurements as well as accurate calculations." "第一原理計算で界面の酸化還元・酸塩基過程を探る","第一原理計算で界面の酸化還元・酸塩基過程を探る","館山 佳尚","館山 佳尚","第38回触媒学会若手会「夏の研修会」","第38回触媒学会若手会「夏の研修会」","2017-08-02","","jpn","oral_presentation","","","","","",""," 近年のスーパーコンピュータ・Linuxクラスターの性能の向上と、第一原理計算ソフトウェアの汎用化から、触媒材料・反応に関する第一原理計算研究が非常に一般的なものになってきた。例えば実験グループにおいても第一原理計算が数多く行われている。しかし触媒反応の微視的機構をより正しくかつ精度よく再現するには、まだまだ理論計算手法のリファインが必須であると考えられる。 本講演では触媒反応に関する第一原理計算アプローチを振り返りながら、今後より複雑な触媒反応を記述する上で必要となるであろう、理論計算手法について紹介する。また当研究室で行っている先端的アプローチについても合わせて紹介する。" "Brute-Force First-Principles Sampling Investigations of Battery Electrolytes and Interfaces","Brute-Force First-Principles Sampling Investigations of Battery Electrolytes and Interfaces","館山 佳尚","館山 佳尚","Materials research by Information Integration Initiative Worksho","Materials research by Information Integration Initiative Worksho","2017-07-27","","jpn","oral_presentation","","","","","","","We have newly implemented multiple MPI parallelization in the Car-Parrinello Molecular dynamics code, CPMD, for efficient free energy calculations, which allows to examine one reaction with only one job. Using the code on the K computer, we elucidated the novel mechanisms on solid electrolyte interphases (SEI) films formed at the electrolyte-electrode interfaces and unusual characteristics of superconcentrated electrolyte in batteries. Recently, we have used this code to carry out high-throughput first-principles calculations for machine-learning analysis as well." "DFT molecular dynamics studies on battery materials: SEI film and superconcentrated electrolyte","DFT molecular dynamics studies on battery materials: SEI film and superconcentrated electrolyte","館山 佳尚","館山 佳尚","FiMPART2017","FiMPART2017","2017-07-09","","jpn","oral_presentation","","","","","","","We investigated the formation mechanisms and the properties of organic and inorganic solid electrolyte interphase (SEI) films, a long standing issue in the battery science, and the superconcentrated electrolytes that attract much attention recently for next-generation electrolytes, by first-principles DFT molecular dynamics (MD) simulations on supercomputers like the K computer in Japan. Regarding the SEI issue, we found a novel mechanism of the VC additive effect on the initial reductive decomposition of EC solvent and then proposed a probable subsequent mechanism with the decomposed products toward the organic SEI formation at the electrode – electrolyte interface which overturns the conventional understandings. Also, the equilibrium properties of SEI films involving inorganic LiF " "First-Principles study on interfaces between sulfide electrolyte and cathode in all solid-state battery","First-Principles study on interfaces between sulfide electrolyte and cathode in all solid-state battery","館山 佳尚, 春山潤, 袖山 慶太郎","館山 佳尚, 春山潤, 袖山 慶太郎","Platform for Advanced Scientific Computing Conference (PASC17)","Platform for Advanced Scientific Computing Conference (PASC17)","2017-06-26","","jpn","oral_presentation","","","","","","","All-solid-state Li-ion batteries have been regarded as promising next-generation batteries. However, large interfacial resistance for ion transport is usually observed even if promising sulfide electrolyte is set on typical oxide cathode. These phenomena have been explained with structural disorder and space-charge layer of Li ion around the interface, though little is known about the atomistic mechanism. Then, we investigated probable heterogeneous interfaces between a sulfide electrolyte (β-Li3PS4) and an oxide cathode (LiCoO2) by DFT+U calculations with some techniques to evaluate the stable matching of incommensurate solid-solid interface and the site-dependent chemical potential of Li ion. The results indicate that the Li depletion can proceed at the beginning of the charge process, " "First-principles study on effects of buffer layer, Li depletion, and ion mixing at interfaces between LiCoO2 and sulfide electrolyte in all-solid-state battery","First-principles study on effects of buffer layer, Li depletion, and ion mixing at interfaces between LiCoO2 and sulfide electrolyte in all-solid-state battery","館山 佳尚, 春山潤, 袖山 慶太郎","館山 佳尚, 春山潤, 袖山 慶太郎","21th International Conference on Solid State Ionics (SSI-21)","21th International Conference on Solid State Ionics (SSI-21)","2017-06-18","","jpn","oral_presentation","","","","","","","All-solid-state Lithium-ion batteries (ASS-LIBs) have been regarded as promising next-generation batteries. Recently, sulfide-based electrolytes have attracted considerable attention because of the high Li-ion conductivities comparable to those of the ordinary organic-liquid electrolytes. However, large interfacial resistance is usually observed if we combine sulfide electrolytes and oxide cathodes [1]. On the other hand, it has been also observed that the interfacial resistance is reduced dramatically by interposing an insulating buffer layer to the interfaces [1]. Compared to these observations, little is known about the atomistic aspects of the solid-solid interfaces in the ASS-LIBs. Therefore, we have investigated those properties such as potential origins of the interfacial resistance" "Extensive investigations of surface properties of ABO3 perovskite materials toward surface machine leaning","Extensive investigations of surface properties of ABO3 perovskite materials toward surface machine leaning","飯塚 将太, Sergey Levchenko, 館山 佳尚, Matthias Scheffler","飯塚 将太, Sergey Levchenko, 館山 佳尚, Matthias Scheffler","2017 International Workshop on Electrified Interfaces for Energy","2017 International Workshop on Electrified Interfaces for Energy","2017-05-18","","jpn","oral_presentation","","","","","","","Toward catalyst or surface informatics study, database of surface properties is of great importance. However, there have been few comprehensive computational investigations of surface properties. We focus on A3+B3+O3-type of ABO3 perovskite materials, and address first- principles calculations of structures, electronic states and defect properties of the several surfaces (surface terminations) that are expected to be stable, by using the fhi-aims code. We pay much attention to keep the same accuracy because it is quite important for the efficient machine learning. We believe that the present results will play sufficient roles for the surface machine learning. This study is carried out in collaboration with Dr. Sergey Levchenko, Dr. Aliaksei Mazheika as well as Prof. Matthias Scheffler in t" "DFT simulation study on CO2 reduction to formic acid at Boron-doped diamond (BDD) surfaces","DFT simulation study on CO2 reduction to formic acid at Boron-doped diamond (BDD) surfaces","豆 茂峰, 飯塚 将太, 栄長泰明, 館山 佳尚","豆 茂峰, 飯塚 将太, 栄長泰明, 館山 佳尚","2017 International Workshop on Electrified Interfaces for Energy","2017 International Workshop on Electrified Interfaces for Energy","2017-05-18","","jpn","oral_presentation","","","","","","","We have investigated CO2 reduction mechanism at typical BDD(111) interfaces with three different types of terminations, namely, H-, OH-, and OH&H-mixed terminations, by using first-principles density functional theory calculations. We found that the hydroxyl hydrogen at surfaces with OH&H-mixed terminations involve in the reaction and act as proton source, which enhances the activity of reduction CO2 to HCOOH. In addition, production of CO is inhibited at all the surfaces, namely, (111) surfaces with H-, OH-, or OH&H-mixed terminations. These results suggest that hydrogen in the termination of BDD play a crucial role to evolve these hydro carbons instead of CO. The present mechanism will give a perspective for CO2 reduction on the semiconductor electrodes." "計算科学技術による蓄電池機構解明・材料設計","計算科学技術による蓄電池機構解明・材料設計","館山 佳尚","館山 佳尚","日本化学会第97春季年会","日本化学会第97春季年会","2017-03-16","","jpn","oral_presentation","","","","","","","There are two major computational approaches to the next-generation battery materials now; (1) large-scale accurate simulations of the microscopic chemical processes for better understanding and future design, and (2) quick screening of potential materials via materials informatics techniques. Here I’ll introduce our recent works along with the former strategy mainly. Developing highly-efficient DFT-based sampling techniques (ex. stat-CPMD code) for supercomputers such as the K computer, we addressed the crucial issues on the electrode-electrolyte interfaces and the electrolytes in the battery field" "stat-CPMDを用いた リチウムイオン電池界面被膜に関する第一原理計算研究","stat-CPMDを用いた リチウムイオン電池界面被膜に関する第一原理計算研究","館山 佳尚","館山 佳尚","重点課題⑤「エネルギーの高効率な創出,変換・貯蔵,利用の新規基盤","重点課題⑤「エネルギーの高効率な創出,変換・貯蔵,利用の新規基盤","2016-12-15","","jpn","oral_presentation","","","","","","","我々が行ったstat-CPMDを用いた リチウムイオン電池界面被膜に関する第一原理計算研究について紹介する。" "第一原理計算による層状化合物MXene負極へのカチオン挿入機構の解析","第一原理計算による層状化合物MXene負極へのカチオン挿入機構の解析","サボバ ルチエ, 袖山 慶太郎, 梶山智司, 大久保將史, 山田淳夫, 館山 佳尚","サボバ ルチエ, 袖山 慶太郎, 梶山智司, 大久保將史, 山田淳夫, 館山 佳尚","第57回電池討論会","第57回電池討論会","2016-11-29","","jpn","oral_presentation","","","","","","","我々が行った第一原理計算による層状化合物MXene負極へのカチオン挿入機構の解析について紹介する。" "DFT molecular dynamics studies on battery materials: SEI film and superconcentrated electrolyte","DFT molecular dynamics studies on battery materials: SEI film and superconcentrated electrolyte","館山 佳尚","館山 佳尚","IWAMSN2016","IWAMSN2016","2016-11-08","","jpn","oral_presentation","","","","","","","I will introduce our recent studies on DFT molecular dynamics studies on battery materials: SEI film and superconcentrated electrolyte." "Surface termination & ion migration of perovskite materials for carrier transport and aging","Surface termination & ion migration of perovskite materials for carrier transport and aging","館山 佳尚","館山 佳尚","ENGE2016","ENGE2016","2016-11-06","","jpn","oral_presentation","","","","","","","I will introduce our recent studies on Surface termination & ion migration of perovskite materials for carrier transport and aging." "計算科学技術支援による蓄電池機構解明と材料設計","計算科学技術支援による蓄電池機構解明と材料設計","館山 佳尚","館山 佳尚","NIMS WEEK 2016","NIMS WEEK 2016","2016-10-20","","jpn","oral_presentation","","","","","","","我々が行っている計算科学技術支援による蓄電池機構解明と材料設計について紹介する。" "色素増感・ペロブスカイト太陽電池界面の電荷移動機構に関する第一原理計算解析","色素増感・ペロブスカイト太陽電池界面の電荷移動機構に関する第一原理計算解析","濱田 幾太郎, 館山 佳尚, 袖山 慶太郎, 大谷 優介","濱田 幾太郎, 館山 佳尚, 袖山 慶太郎, 大谷 優介","第3回「京」を中核とするHPCIシステム利用研究課題 成果報告会","第3回「京」を中核とするHPCIシステム利用研究課題 成果報告会","2016-10-20","","jpn","oral_presentation","","","","","","","我々が行っている色素増感・ペロブスカイト太陽電池界面の電荷移動機構に関する第一原理計算解析について紹介する。" " ボロンドープダイヤモンド(Boron-Doped Diamond:BDD)電極によるOHラジカル発生機構","ボロンドープダイヤモンド(Boron-Doped Diamond:BDD)電極によるOHラジカル発生機構","館山 佳尚, Zdenek Futera, 渡辺剛志, 栄長泰明","館山 佳尚, Zdenek Futera, 渡辺剛志, 栄長泰明","第118回触媒討論会","第118回触媒討論会","2016-09-21","","jpn","oral_presentation","","","","","","","我々が行っているボロンドープダイヤモンド(Boron-Doped Diamond:BDD)電極によるOHラジカル発生機構の第一原理計算解析について紹介する。" "二次電池電解液・電極界面の計算材料科学","二次電池電解液・電極界面の計算材料科学","館山 佳尚","館山 佳尚","日本物理学会2016年秋季大会","日本物理学会2016年秋季大会","2016-09-13","","jpn","oral_presentation","","","","","","","我々が行っている二次電池電解液・電極界面の計算材料科学について紹介する。" "Ab-initio MD simulations of redox reactions of liquid electrolytes and SEI formation ","Ab-initio MD simulations of redox reactions of liquid electrolytes and SEI formation ","館山 佳尚","館山 佳尚","IMLB2016 (18th International Meeting on Lithium Batteries)","IMLB2016 (18th International Meeting on Lithium Batteries)","2016-06-19","","jpn","oral_presentation","","","","","","","Atomistic understanding of solid electrolyte interphase (SEI) formed at the interface between electrode and liquid electrolyte is still an issue of great importance. However, difficulties in experimental in-situ observations of the buried interfaces and simulations considering the liquid dynamics (fluctuation) and reaction have inhibited the progress of elucidation. We have addressed such issues by means of accurate large-scale ab-initio molecular dynamics (MD) samplings and free energy calculations on a huge supercomputer." "スパコンを用いた二次電池電解液・電極界面の微視的機構研究 ","スパコンを用いた二次電池電解液・電極界面の微視的機構研究 ","館山 佳尚","館山 佳尚","第381回電池技術委員会","第381回電池技術委員会","2016-06-17","","jpn","oral_presentation","","","","","","","二次電池の電解液・電極界面は、イオン輸送抵抗、電解液の酸化還元分解、SEI(Solid Electrolyte Interphase)膜形成・分解など、電池の性能と信頼性を左右する主要過程の反応場となっています。しかし界面における電子・原子の挙動は、実験によるその場観察がまだ難しいため、いまだによく分かっていません。そこで我々は、スパコンによる第一原理分子動力学シミュレーションを駆使して、電解液・電極界面で起こっている現象の微視的機構の解明に取り組みました。" "Ab-initio MD simulations of redox reactions of liquid electrolytes and SEI formation","Ab-initio MD simulations of redox reactions of liquid electrolytes and SEI formation","館山 佳尚","館山 佳尚","CPMD2016 Conference","CPMD2016 Conference","2016-05-18","","jpn","oral_presentation","","","","","","","We focused on the thermodynamics as well as the kinetics of the possible processes. We used DFT-based Car-Parrinello MD (CPMD) with explicit solvent molecules for the equilibrium properties, and carried out the free energy profile calculations along the reaction pathways using the blue-moon ensemble technique with constraint CPMD. We considered Li+ in only EC solvent (EC system) and in EC solvent with a VC additive (EC/VC system) to elucidate the additive effect. The supercells involving 32 EC molecules or 31 EC with one VC molecules, with one Li atom, were adopted. It is cubic box with a length of 15.24 Å to reproduce the experimental EC density, and periodic boundary condition is applied for keeping the liquid density constant. We used the Nosé thermostat with a temperature " "「京」を用いた蓄電池界面・SEI膜の第一原理計算解析","「京」を用いた蓄電池界面・SEI膜の第一原理計算解析","館山 佳尚","館山 佳尚","第1 回SPRUC 分野融合研究(実用)ワークショップ","第1 回SPRUC 分野融合研究(実用)ワークショップ","2016-03-28","","jpn","oral_presentation","","","","","","","「京」を用いた蓄電池界面・SEI膜の第一原理計算解析について紹介する。" "Theoretical study on surface and ion migration of perovskite materials in Perovskite Solar Cell (PSC)","Theoretical study on surface and ion migration of perovskite materials in Perovskite Solar Cell (PSC)","館山 佳尚","館山 佳尚","MANA International Symposium 2016","MANA International Symposium 2016","2016-03-09","","jpn","oral_presentation","","","","","","","I will introduce Theoretical study on surface and ion migration of perovskite materials in Perovskite Solar Cell (PSC)." "DFT samplings reveal atomistic mechanisms around electrolyte-electrode interfaces in batteries","DFT samplings reveal atomistic mechanisms around electrolyte-electrode interfaces in batteries","館山 佳尚","館山 佳尚","Japanese Swiss Energy Materials Workshop","Japanese Swiss Energy Materials Workshop","2016-03-07","","jpn","oral_presentation","","","","","","","I introduce our recent works on DFT samplings reveal atomistic mechanisms around electrolyte-electrode interfaces in batteries." "重点課題名:⑤エネルギーの高効率な創出、変換・貯蔵、利用の新規基盤技術の開発","重点課題名:⑤エネルギーの高効率な創出、変換・貯蔵、利用の新規基盤技術の開発","館山 佳尚","館山 佳尚","産応協、CMSI、ポスト京重点課題5・6・7合同 産学官連携シンポジ","産応協、CMSI、ポスト京重点課題5・6・7合同 産学官連携シンポジ","2016-02-24","","jpn","oral_presentation","","","","","","","重点課題⑤エネルギーの高効率な創出、変換・貯蔵、利用の新規基盤技術の開発について紹介する。" "電極界面における電解液反応シミュレーション 〜リチウムイオン2次電池の安全性・機能性向上に向けて〜","電極界面における電解液反応シミュレーション 〜リチウムイオン2次電池の安全性・機能性向上に向けて〜","館山 佳尚","館山 佳尚","文部科学省 元素戦略プロジェクト<研究拠点形成型>/大型研究施設 ","文部科学省 元素戦略プロジェクト<研究拠点形成型>/大型研究施設 ","2016-01-22","","jpn","oral_presentation","","","","","","","我々のグループの電極界面における電解液反応シミュレーションについて紹介する。" "偏光X 線を用いた放射光光電子分光","偏光X 線を用いた放射光光電子分光","大橋 直樹, 大澤 健男, 上田 茂典, 鈴木基寛, ウィリアムズ ジェシー ロバート, 館山 佳尚","大橋 直樹, 大澤 健男, 上田 茂典, 鈴木基寛, ウィリアムズ ジェシー ロバート, 館山 佳尚","文部科学省 元素戦略プロジェクト<研究拠点形成型>/大型研究施設 ","文部科学省 元素戦略プロジェクト<研究拠点形成型>/大型研究施設 ","2016-01-21","","jpn","oral_presentation","","","","","","","偏光X 線を用いた放射光光電子分光の応用事例として、部分状態密度の理論的・実験的評価に向けた検討結果を報告する。特に、DFT計算で算出される投影状態密度(PDOS)と偏光X線を使ったXPSスペクトルとの比較を行った結果を論じる。" "二次電池内プロセスに関する第一原理計算研究の展開","二次電池内プロセスに関する第一原理計算研究の展開","館山 佳尚","館山 佳尚","TCCI第5回産学連携シンポジウム","TCCI第5回産学連携シンポジウム","2016-01-19","","jpn","oral_presentation","","","","","","","二次電池内プロセスに関する第一原理計算研究の展開について報告する。" "Elucidation of complicated reactions around electrolyte – electrode interfaces in Li-ion battery","Elucidation of complicated reactions around electrolyte – electrode interfaces in Li-ion battery","館山 佳尚","館山 佳尚","Pacifichem2015","Pacifichem2015","2015-12-15","","jpn","oral_presentation","","","","","","","We have then addressed providing electronic and atomistic mechanisms around electrolyte-electrode interfaces in LIBs, in collaboration with experimentalists, by using the advanced DFT simulations. Since LIB usually involves both electronics and ionics, dynamics and sampling is more crucial than the electronic states accuracy. Thus, we focused on efficient samplings and accurate calculations of free energies with rather standard DFT framework. " "Semiconductor-water interfaces investigated by first principles calculations of boron doped diamond","Semiconductor-water interfaces investigated by first principles calculations of boron doped diamond","館山 佳尚","館山 佳尚","Pacifichem2015","Pacifichem2015","2015-12-15","","jpn","oral_presentation","","","","","","","Semiconductor/electrolyte interfaces represent one of the most challenging systems for theoretical and computational description because of their complexity, nevertheless their detail understanding is crucial for modern electrochemistry, catalysis and batteries. Here, we investigated water interfaces of semiconductive boron-doped diamond (BDD) terminated by hydrogen (Figure), oxygen, and hydroxyl groups by using density functional theory (DFT)-based molecular dynamics [1]" "固液界面反応に関する第一原理計算アプローチ:現状と展望","固液界面反応に関する第一原理計算アプローチ:現状と展望","館山 佳尚","館山 佳尚","第6回真空・表面科学若手研究会","第6回真空・表面科学若手研究会","2015-12-04","","jpn","oral_presentation","","","","","","","DFT計算の基礎を復習した後、固液界面・酸化還元・電気化学反応を取り扱うための理論的拡張を説明する。さらに京コンピュータ等を用いた二次電池、太陽電池、光触媒などの微視的機構解明について解説する。" "DFT samplings reveal atomistic mechanisms in electrolyte and at electrode interface in Li-ion battery","DFT samplings reveal atomistic mechanisms in electrolyte and at electrode interface in Li-ion battery","館山 佳尚","館山 佳尚","MANA-RSC symposium: Materials for Energy Generation and Storage","MANA-RSC symposium: Materials for Energy Generation and Storage","2015-10-15","","jpn","oral_presentation","","","","","","","We carried out DFT-MD free energy calculations of the reductive decompositions of the carbonate-based electrolytes on the 10 peta-flops K computer in Japan, focusing on the thermodynamics as well as the kinetics1,2." "第一原理計算に基づく表面・界面の計算科学","第一原理計算に基づく表面・界面の計算科学","館山 佳尚","館山 佳尚","関西接着ワークショップ 2015年度 第2回研究会","関西接着ワークショップ 2015年度 第2回研究会","2015-10-14","","jpn","oral_presentation","","","","","","","界面に対する定量的計算手法を説明し、応用例としてTiO2/H2O界面の構造および電子状態、リチウムイオン電池負極ー有機電解液界面の微視的現象を紹介する。" "DFT-MD Study on Formation Processes of Solid Electrolyte Interphase at Negative Electrode Interfaces in Lithium-Ion Battery","DFT-MD Study on Formation Processes of Solid Electrolyte Interphase at Negative Electrode Interfaces in Lithium-Ion Battery","館山 佳尚","館山 佳尚","The 66th Annual Meeting of the International Society of Electroc","The 66th Annual Meeting of the International Society of Electroc","2015-10-04","","jpn","oral_presentation","","","","","","","It is well known that most of those properties are governed by the quality of solid electrolyte interphase (SEI) film formed on the interface between negative electrode and organic electrolyte. However, the reaction mechanisms around electrolyte-electrode interfaces have not been fully understood yet on the atomic scale due to the difficulty in experimental in-situ observation. Then, we have addressed such unresolved issues by using DFT-MD sampling with sufficient accuracy" "固液界面酸化還元反応の第一原理計算解析","固液界面酸化還元反応の第一原理計算解析","館山 佳尚","館山 佳尚","電気化学界面シミュレーションコンソーシアム","電気化学界面シミュレーションコンソーシアム","2015-09-29","","jpn","oral_presentation","","","","","","","DFT計算の基礎を復習した後、固液界面・酸化還元・電気化学反応を取り扱うための理論的拡張を説明する。さらに京コンピュータ等を用いた二次電池、太陽電池、光触媒などの微視的機構解明について解説する。" "金属-CeO2表面系における水吸着・解離に関する第一原理計算研究","金属-CeO2表面系における水吸着・解離に関する第一原理計算研究","館山 佳尚, サボバ ルチエ, Stefano Fabris","館山 佳尚, サボバ ルチエ, Stefano Fabris","第116回触媒討論会","第116回触媒討論会","2015-09-16","","jpn","oral_presentation","","","","","","","水性ガスシフト反応やCO酸化反応の素過程理解を目標に、金属-CeO2系表面界面の水吸着・解離について電子相関を考慮した第一原理計算研究を実行した。今回Cuに担持されたCeO2薄膜モデル系を取り扱いCeO2表面上の水吸着・分解に関する反応サイト依存性を計算した。さらに金属とCeO2の間の電荷移動と反応サイトの相関について議論した。" "A novel Double-QM/MM method for donor-acceptor electron transfer in solution","A novel Double-QM/MM method for donor-acceptor electron transfer in solution","館山 佳尚, フテラ ズデニェク, 袖山 慶太郎","館山 佳尚, フテラ ズデニェク, 袖山 慶太郎","Psi-k 2015 Conference","Psi-k 2015 Conference","2015-09-06","","jpn","oral_presentation","","","","","","","We developed a double-quantum mechanical / molecular mechanical (d-QM/MM) method for investigation of outer-sphere electron transfer (ET) processes between donor and acceptors (DA) in condensed matter [1]." "Formation Processes of Solid Electrolyte Interphase at Electrode Interfaces in Lithium-Ion Battery","Formation Processes of Solid Electrolyte Interphase at Electrode Interfaces in Lithium-Ion Battery","館山 佳尚, 後瀉 敬介, 袖山 慶太郎, 奥野 幸洋","館山 佳尚, 後瀉 敬介, 袖山 慶太郎, 奥野 幸洋","Psi-k 2015 Conference","Psi-k 2015 Conference","2015-09-06","","jpn","oral_presentation","","","","","","","Several key properties are governed by the quality of solid electrolyte interphase (SEI) formed on the interface between negative electrode and organic electrolyte. However, the interfacial processes have not been fully understood yet due to the difficulty in experimental observation. We have addressed such unresolved issues by using DFT-MD sampling techniques." "Lithium space-charge layer at interfaces between oxide cathode and sulfide electrolyte for interfacial resistance in all solid state lithium ion battery: A DFT simulation study","Lithium space-charge layer at interfaces between oxide cathode and sulfide electrolyte for interfacial resistance in all solid state lithium ion battery: A DFT simulation study","館山 佳尚","館山 佳尚","The 11th Pacific Rim Conference of Ceramic Societies (PACRIM11)","The 11th Pacific Rim Conference of Ceramic Societies (PACRIM11)","2015-08-30","","jpn","oral_presentation","","","","","","","Although new inorganic (mainly sulfide) electrolyte materials with fast ion diffusion have been developed recently, the interfacial resistance is still an issue of significance. Then, we studied the mechanism of the interfacial resistance for its improvement, by using density functional theory (DFT) +U calculations. We focused on a typical ASS-LIB system with LiCoO2 oxide cathode and β-Li3PS4 sulfide electrolyte, and examined the effect of LiNbO3 buffer layer as well." "Surface termination & ion migration of perovskite materials","Surface termination & ion migration of perovskite materials","館山 佳尚","館山 佳尚","CECAM workshop: Perovskite solar cells: the quest for a theoreti","CECAM workshop: Perovskite solar cells: the quest for a theoreti","2015-08-25","","jpn","oral_presentation","","","","","","","Here I introduce our recent studies on the termination effects of (110), (001), (100) and (101) surfaces of tetragonal MAPbI3 toward organic hole transport materials (HTMs) [1], and the interface states with model oxide anodes, by density functional theory based supercell calculations with PBE and vdW-DF2-B86R functionals" "固液界面・酸化還元・電気化学反応の第一原理計算","固液界面・酸化還元・電気化学反応の第一原理計算","館山 佳尚","館山 佳尚","第55回分子科学若手の会夏の学校","第55回分子科学若手の会夏の学校","2015-08-17","","jpn","oral_presentation","","","","","","","エネルギー変換に関する微視的機構の解明や新しい電池・触媒の設計・開発は物理・化学・材料科学をまたぐ最重要課題の一つです。このエネルギー変換の根元は酸化還元過程に帰着させることができます(光励起も重要ですが、電子移動がなければエネルギーを取り出せません)。また反応場として界面が重要な役割を果たします。本分科会では、この課題に焦点をあて、エネルギー・環境関連の研究・開発に興味のある若手、特に理論計算シミュレーションを念頭におく諸君に、理解しておいてもらいたい事柄をまとめて講義することにしました。" "DFT study on surface and interface states of tetragonal CH3NH3PbI3 for understanding interfacial charge transfer","DFT study on surface and interface states of tetragonal CH3NH3PbI3 for understanding interfacial charge transfer","館山 佳尚","館山 佳尚","第10回 NIMS GREENシンポジウム","第10回 NIMS GREENシンポジウム","2015-06-25","","jpn","oral_presentation","","","","","","","Many characters of bulk CH3NH3PbI3 (MAPbI3) such as small effective masses of the photo-excited carriers have been elucidated so far, whereas little is known about surface and interface properties of MAPbI3 yet due to the difficulty in the observations. Here we investigated surfaces of tetragonal MAPbI3 toward organic hole transport materials (HTMs) and the interfaces with model oxide anodes (ex. TiO2 surface), by density functional theory (DFT) based supercell calculations with PBE and rev-vdW-DF2 functionals." "DFT-MD study on highly concentrated Li-salt electrolyte: A new class of electrolyte for batteries","DFT-MD study on highly concentrated Li-salt electrolyte: A new class of electrolyte for batteries","館山 佳尚, 袖山 慶太郎","館山 佳尚, 袖山 慶太郎","Workshop on Materials Science for Energy Storage","Workshop on Materials Science for Energy Storage","2015-05-11","","jpn","oral_presentation","","","","","","","In order to explore the underlying mechanisms of highly concentrated Li-salt electrolyte, we investigated low (LC) and high (HC) concentration systems of LiN(SO2CF3)2 (Li-TFSA) salt in acetonitrile (AN) solution by DFT-MD sampling techniques with extra electron(s) on the 10 petaflops “K computer” in Japan [2,3]." "DFT study on surface and interface states of tetragonal CH3NH3PbI3 for understanding interfacial charge transfer","DFT study on surface and interface states of tetragonal CH3NH3PbI3 for understanding interfacial charge transfer","館山 佳尚, 春山 潤, 韓 礼元, 袖山 慶太郎","館山 佳尚, 春山 潤, 韓 礼元, 袖山 慶太郎","International Conference on Hybrid and Organic Photovoltaics (HO","International Conference on Hybrid and Organic Photovoltaics (HO","2015-05-10","","jpn","oral_presentation","","","","","","","Many characters of bulk CH3NH3PbI3 (MAPbI3) such as small effective masses of the photo-excited carriers have been elucidated so far, whereas little is known about surface and interface properties of MAPbI3 yet due to the difficulty in the observations. Here we investigated surfaces of tetragonal MAPbI3 toward organic hole transport materials (HTMs) and the interfaces with model oxide anodes (ex. TiO2 surface), by density functional theory (DFT) based supercell calculations with PBE and rev-vdW-DF2 functionals." "Co-sensitizer effect of black (N749) dye by DFT molecular dynamics investigations of TiO2(101)/black dye/acetonitrile interfaces","Co-sensitizer effect of black (N749) dye by DFT molecular dynamics investigations of TiO2(101)/black dye/acetonitrile interfaces","館山 佳尚, 大谷 優介, 児玉 小春, 韓 礼元, 袖山 慶太郎","館山 佳尚, 大谷 優介, 児玉 小春, 韓 礼元, 袖山 慶太郎","International Conference on Hybrid and Organic Photovoltaics (HO","International Conference on Hybrid and Organic Photovoltaics (HO","2015-05-10","","jpn","oral_presentation","","","","","","","Although perovskite solar cells attract significant attention now, fundamental mechanisms of conventional dye-sensitized solar cells (DSC) have not been fully understood yet, and still deserve being investigated. Here we addressed a question why Ru 749 dye (black dye:BD) gives better efficiency than the others, which is useful for further improvement of DSCs. We examined stable structures and photoexcitation character of BD adsorption to TiO2 anatase (101) interface immersed in bulk acetonitrile (AN) solution, a most representative electrode interface in DSCs." "リチウムイオン電池電極ー電解質界面の第一原理計算研究","リチウムイオン電池電極ー電解質界面の第一原理計算研究","館山 佳尚","館山 佳尚","講演会「計算と実験による蓄電池材料研究」","講演会「計算と実験による蓄電池材料研究」","2015-04-24","","jpn","oral_presentation","","","","","","","第一原理ダイナミクス・サンプリング解析による リチウムイオン電池内反応機構の解明の最近の研究を紹介した。" "DFT-MD Simulations Reveal Novel Mechanisms of Electrolyte and Electrode Interface in Li-ion Battery","DFT-MD Simulations Reveal Novel Mechanisms of Electrolyte and Electrode Interface in Li-ion Battery","館山 佳尚","館山 佳尚","MOST-NIMS Workshop","MOST-NIMS Workshop","2015-04-21","","jpn","oral_presentation","","","","","","","These properties are mainly governed by the quality of solid electrolyte interphase (SEI) film on the interface between electrode and electrolyte. The reductive decomposition of the electrolyte molecules plays a crucial role in the SEI formation. Slight change of the electrolyte component often exhibits a large impact on the SEI quality. However, the microscopic mechanisms in electrolyte and at electrode interface have not been fully understood yet. We have addressed such important issues by using the advanced DFT simulation techniques." "LIB の酸化還元反応、電極被膜、イオン伝導に対する第一原理計算アプローチ","LIB の酸化還元反応、電極被膜、イオン伝導に対する第一原理計算アプローチ","館山 佳尚","館山 佳尚","電気化学界面シミュレーションコンソーシアム設立シンポジウム","電気化学界面シミュレーションコンソーシアム設立シンポジウム","2015-04-16","","jpn","oral_presentation","","","","","","","「京」上での第一原理統計サンプリングシミュレーションによる、LIB の酸化還元反応、電極被膜、イオン伝導の微視的機構解明に関する最近の研究を紹介。" "第一原理統計力学による太陽電池・光触媒界面の動作環境下電荷移動・励起過程の解明","第一原理統計力学による太陽電池・光触媒界面の動作環境下電荷移動・励起過程の解明","館山 佳尚","館山 佳尚","JST CREST・さきがけ「相界面」研究領域第1回公開シンポジウム","JST CREST・さきがけ「相界面」研究領域第1回公開シンポジウム","2015-03-30","","jpn","oral_presentation","","","","","","","JSTさきがけにおける研究成果全体を紹介する。" "ドナー・アクセプター間電子移動反応に向けたdouble QM/MM法開発","ドナー・アクセプター間電子移動反応に向けたdouble QM/MM法開発","館山 佳尚, フテラ ズデニェク, 袖山 慶太郎","館山 佳尚, フテラ ズデニェク, 袖山 慶太郎","日本物理学会第70回年次大会","日本物理学会第70回年次大会","2015-03-21","","jpn","oral_presentation","","","","","","","我々はdouble QM/MM手法を開発した。この手法はconstraint DFT と同じコンセプトを有するが、ドナー領域とアクセプター領域の区別がより明確にできるという利点を持つ。" "サブ課題B 研究事例「「京」を用いたリチウムイオン電池内機構の第一原理シミュレーション」","サブ課題B 研究事例「「京」を用いたリチウムイオン電池内機構の第一原理シミュレーション」","館山 佳尚","館山 佳尚","文部科学省 「エネルギーの高効率な創出,変換・貯蔵,利用の新規基","文部科学省 「エネルギーの高効率な創出,変換・貯蔵,利用の新規基","2015-03-10","","jpn","oral_presentation","","","","","","","「京」を用いたリチウムイオン電池内機構の第一原理シミュレーションについて紹介。" "DFT-MD Simulations Reveal Novel Mechanisms of Electrolyte and Electrode Interface in Li-Ion Battery","DFT-MD Simulations Reveal Novel Mechanisms of Electrolyte and Electrode Interface in Li-Ion Battery","館山 佳尚","館山 佳尚","UNISTRA-NIMS Joint Seminar","UNISTRA-NIMS Joint Seminar","2015-01-26","","jpn","oral_presentation","","","","","","","The reductive decomposition of the electrolyte molecules plays a crucial role in the SEI formation. Slight change of the electrolyte component often exhibits a large impact on the SEI quality. However, the microscopic mechanisms in electrolyte and at electrode interface have not been fully understood yet. We have addressed such important issues by using the advanced DFT simulation techniques." "ダイヤモンド電極の化学反応性の第一原理シミュレーション","ダイヤモンド電極の化学反応性の第一原理シミュレーション","館山 佳尚","館山 佳尚","ニューダイヤモンドフォーラム平成26年度第3回研究会","ニューダイヤモンドフォーラム平成26年度第3回研究会","2015-01-16","","jpn","oral_presentation","","","","","","","本研究ではボロンドープダイヤモンド電極/水界面の電子状態をベースにした化学反応性、特にボロンドープ濃度依存性や表面終端依存性、に焦点をあて、第一原理分子動力学(DFT-MD)シミュレーションを用いて解析を行った[1,2]。" "第一原理ダイナミクス・サンプリング解析による リチウムイオン電池内反応機構の解明","第一原理ダイナミクス・サンプリング解析による リチウムイオン電池内反応機構の解明","館山 佳尚","館山 佳尚","近畿化学協会コンピュータ化学部会 公開講演会","近畿化学協会コンピュータ化学部会 公開講演会","2015-01-15","","jpn","oral_presentation","","","","","","","第一原理ダイナミクス・サンプリング解析による リチウムイオン電池内反応機構の解明の最近の研究を紹介した。" "Novel reaction mechanism of Lithium-ion battery electrolyte by DFT free energy calculation with parallel blue-moon ensemble on K computer","Novel reaction mechanism of Lithium-ion battery electrolyte by DFT free energy calculation with parallel blue-moon ensemble on K computer","館山 佳尚","館山 佳尚","International Symposium on Computics: Quantum Simulation and Des","International Symposium on Computics: Quantum Simulation and Des","2014-12-01","","jpn","oral_presentation","","","","","","","Solid electrolyte interphase (SEI) formed through the reductive decomposition of electrolyte molecules plays a crucial role in the performance and stability of lithium-ion battery (LIB), a key technology for today" "Adsorption, Excitation and Charge Transfer of Black Dye at TiO2 Anatase/Acetonitrile Interface in DSC","Adsorption, Excitation and Charge Transfer of Black Dye at TiO2 Anatase/Acetonitrile Interface in DSC","館山 佳尚, 大谷 優介, 韓 礼元, 袖山 慶太郎","館山 佳尚, 大谷 優介, 韓 礼元, 袖山 慶太郎","The 2nd International Symposium on the Functionality of Organize","The 2nd International Symposium on the Functionality of Organize","2014-11-27","","jpn","oral_presentation","","","","","","","Although the organic-inorganic hybrid perovskites have emerged as solar cells with higher efficiency, the interfacial chemistry of conventional Ru dyes at TiO2 - acetonitrile interfaces in dye-sensitized solar cells (DSCs) is still an issue of fundamental importance. We then investigated stable structures and photoexcitation character of Black Dye (BD; Ru N749 dye) adsorption to TiO2 anatase (101) interface immersed in bulk acetonitrile (AN) solution, a most representative DSC system. Density functional theory based molecular dynamics (DFT-MD) with explicit solvent molecules was used to take into account the fluctuations of solvation shells and adsorbed molecules. We have also combined time-dependent DFT calculations of the excitation energies and oscillator strengths for the discussion o" "全固体電池表面界面の第一原理計算解析","全固体電池表面界面の第一原理計算解析","館山 佳尚","館山 佳尚","物性研究所計算物質科学研究センター 第4回シンポジウム・物性研スー","物性研究所計算物質科学研究センター 第4回シンポジウム・物性研スー","2014-11-12","","jpn","oral_presentation","","","","","","","我々は現在固液界面に焦点を当てた電池内部の機構解明を行っているが、上記の安全性の観点に加え、固液界面と固固界面の相違点と類似点の探索という基礎的観点から、全固体電池に関連する研究もスタートさせた。その中で(1)”全固体リチウム二次電池内の硫化物電解質―遷移金属酸化物正極界面のリチウムイオン状態”及び(2)”ペロブスカイト型太陽電池のペロブスカイト材料表面終端と界面ホール輸送”に関する世界初の第一原理計算解析について紹介する。" "DFT-MD blue-moon ensemble study on reductive decomposition of carbonated-based solvent in lithium ion battery","DFT-MD blue-moon ensemble study on reductive decomposition of carbonated-based solvent in lithium ion battery","館山 佳尚, 後瀉敬介, 袖山 慶太郎, 奥野幸洋","館山 佳尚, 後瀉敬介, 袖山 慶太郎, 奥野幸洋","International Symposium on Extended Molecular Dynamics and Enhan","International Symposium on Extended Molecular Dynamics and Enhan","2014-11-10","","jpn","oral_presentation","","","","","","","Solid electrolyte interphase (SEI) formed through the reductive decomposition of electrolyte molecules plays a crucial role in the performance and stability of lithium-ion battery (LIB). Here we investigated the additive effects on the reductive decomposition, using a typical electrolyte system with ethylene carbonate (EC) solvent and vinylene carbonate (VC) additive." "Adsorption, Excitation and Charge Transfer of Black Dye at TiO2 Anatase/Acetonitrile Interface in DSC","Adsorption, Excitation and Charge Transfer of Black Dye at TiO2 Anatase/Acetonitrile Interface in DSC","館山 佳尚, 大谷 優介, 児玉 小春, 韓 礼元, 袖山 慶太郎","館山 佳尚, 大谷 優介, 児玉 小春, 韓 礼元, 袖山 慶太郎","計算分子科学研究拠点 第5回研究会","計算分子科学研究拠点 第5回研究会","2014-10-17","","jpn","oral_presentation","","","","","","","Interfacial chemistry of conventional Ru dyes at TiO2 - acetonitrile interfaces in dye-sensitized solar cells (DSCs) is still an issue of fundamental importance. We then investigated stable structures and photoexcitation character of Black Dye (BD; Ru N749 dye) adsorption to TiO2 anatase (101) interface immersed in bulk acetonitrile (AN) solution, a most representative DSC system. Density functional theory based molecular dynamics (DFT-MD) with explicit solvent molecules was used to take into account the fluctuations of solvation shells and adsorbed molecules. We have also combined time-dependent DFT calculations of the excitation energies and oscillator strengths for the discussion of the level alignment associated with the interfacial electron transfer." "「リチウムイオン電池」 〜高性能化と高安全性の両立に向けた取り組み〜","「リチウムイオン電池」 〜高性能化と高安全性の両立に向けた取り組み〜","館山 佳尚","館山 佳尚","“「京」で革新するエネルギー創成”記者勉強会","“「京」で革新するエネルギー創成”記者勉強会","2014-10-15","","jpn","oral_presentation","","","","","","","私たちは高精度計算が可能な第一原理分子動力学法と化学反応の自由エネルギー計算手法を融合させた計算技術を世界で初めてLIBに適用し、典型的な電解液内での還元分解過程とSEI膜の素材となる重合過程を原子・分子レベルで明らかにしました。発見した反応機構はいまだに謎が多いLIBの電解液分解と SEI膜形成過程の理解を増進するものとなっています。" "電解質の計算物質科学:次世代蓄電池に向けて","電解質の計算物質科学:次世代蓄電池に向けて","館山 佳尚","館山 佳尚","触媒・電池元素戦略研究拠点 第5回公開シンポジウム","触媒・電池元素戦略研究拠点 第5回公開シンポジウム","2014-10-14","","jpn","oral_presentation","","","","","","","1:イントロダクション 2:カーボネート電解液の添加剤効果の新機構 (Project A) 3:高濃度リチウム塩電解液の化学 (Project B) 4:固体電解質の界面抵抗起源 (Project C) 5:まとめ " "次世代二次電池システムの理論計算設計","次世代二次電池システムの理論計算設計","館山 佳尚","館山 佳尚","第3回TCCIインフォーマルミーティング","第3回TCCIインフォーマルミーティング","2014-10-12","","jpn","oral_presentation","","","","","","","二次電池は電極、電解液(質)およびそれらの界面で構成されており、それらの中で電子輸送およびイオン輸送の両者が行われている。このような系を取り扱うには、凝縮系や表面界面系に適したDFT電子状態計算手法、さらに古典力場や連続体モデル等の併用が必要不可欠である。また電圧印加といった充放電環境の再現も必要となってくる。本課題では「京」重点課題「エネルギー変換の界面科学」で開発してきた凝縮系向けの計算コードをベースにポスト「京」での応用計算実行を目指した更なるプログラム開発・最適化を行い、最終的には古典力場や連続対近似も組み合わせて電池を丸ごと考慮した二次電池シミュレータの構築などにも取り組む。それと同時に、すでに緊急の課題である、電極ー電解液界面被膜(SEI膜)の微視的機構、金属負極の問題、電極材料や電解液組成の最適化および全固体・空気電池の反応メカニズムなどについても解明を進めて行く。" "第一原理MDを用いた電池・触媒界面状態および反応のオペランド解析","第一原理MDを用いた電池・触媒界面状態および反応のオペランド解析","館山 佳尚","館山 佳尚","放射光学会第7回若手研究会:最先端オペランド観測で明らかになる物","放射光学会第7回若手研究会:最先端オペランド観測で明らかになる物","2014-09-29","","jpn","oral_presentation","","","","","","","界面酸化還元過程を最初から最後まで高精度にシミュレーションすることは、余りに複雑過ぎて現状では不可能です。しかし今後のハイパフォーマンスコンピューティング(「京」や「ポスト京」)の発展を見据えて計算手法を整備して行くとともに、個々の過程について理解を深めて行くことは重要であると考えられます。このようなコンセプトから、我々は色素増感・ペロブスカイト太陽電池、リチウムイオン電池、燃料電池、光触媒、電極触媒の固液界面状態および反応の第一原理分子動力学(MD)サンプリングを主に用いた理論解析にここ数年取り組んできました。本講演ではそれらについてご紹介します。" "Theoretical Study on Reactions in Electrolyte and at Electrode-Electrolyte Interface in Lithium Ion Battery","Theoretical Study on Reactions in Electrolyte and at Electrode-Electrolyte Interface in Lithium Ion Battery","館山 佳尚","館山 佳尚","The 10th Japan-France Joint Seminar on Battery","The 10th Japan-France Joint Seminar on Battery","2014-09-22","","jpn","oral_presentation","","","","","","","We have investigated microscopic issues related to electrolytes and electrode-electrolyte interfaces in LIBs, by using advanced DFT simulation techniques such as molecular dynamics sampling, blue-moon ensemble and DFT+U framework on supercomputers including the K computer. We theoretically elucidated the reductive reaction mechanisms of the molecules in the EC/VC electrolyte and the acetonitrile solvent with super-concentrated Li-salts, toward the SEI formation. We also clarified the Li-ion behavior at oxide cathode/sulfide electrolyte interfaces and the effect of the buffer layers in a typical all-solid-state LIB. These atomistic understandings will contribute to the further improvement of the secondary battery technology." "DFT-MD Simulations Reveal Novel Reaction Mechanisms of Electrolyte toward SEI formation in LIB","DFT-MD Simulations Reveal Novel Reaction Mechanisms of Electrolyte toward SEI formation in LIB","館山 佳尚","館山 佳尚","The 3rd TYC Energy Materials Workshop","The 3rd TYC Energy Materials Workshop","2014-09-10","","jpn","oral_presentation","","","","","","","We have addressed such important issues by using the advanced DFT simulation techniques. We carried out DFT-MD free energy calculations of the reductive decompositions of the carbonate-based electrolytes on the K computer, focusing on the thermodynamics as well as the kinetics. The reaction mechanisms in a novel type of superconcentrated electrolytes were examined with the same techniques as well. We then succeeded in theoretically elucidating the reductive reaction mechanisms of the electrolyte molecules for the first time. Recently, we have also investigated the Li-ion behavior at oxide cathode/solid electrolyte interfaces and the effect of the buffer layers. These new findings will contribute to the development of LIBs with higher performance and better safety." "Adsorption, Excitation and Charge Transfer of Black Dye at TiO2 Anatase/Acetonitrile Interface in DSC","Adsorption, Excitation and Charge Transfer of Black Dye at TiO2 Anatase/Acetonitrile Interface in DSC","館山 佳尚, 大谷 優介, 児玉 小春, 韓 礼元, 袖山 慶太郎","館山 佳尚, 大谷 優介, 児玉 小春, 韓 礼元, 袖山 慶太郎","65th Annual Meeting of the International Society of Electrochemi","65th Annual Meeting of the International Society of Electrochemi","2014-08-31","","jpn","oral_presentation","","","","","","","Although the organic-inorganic hybrid perovskites have emerged as solar cells with higher efficiency, the interfacial chemistry of conventional Ru dyes at TiO2 - acetonitrile interfaces in dye-sensitized solar cells (DSCs) is still an issue of fundamental importance. We then investigated stable structures and photoexcitation character of Black Dye (BD; Ru N749 dye) adsorption to TiO2 anatase (101) interface immersed in bulk acetonitrile (AN) solution, a most representative DSC system. Density functional theory based molecular dynamics (DFT-MD) with explicit solvent molecules was used to take into account the fluctuations of solvation shells and adsorbed molecules. We have also combined time-dependent DFT calculations of the excitation energies and oscillator strengths for the discussion o" "スーパーコンピュータが先導する産学連携による材料開発〜リチウムイオン電池〜","スーパーコンピュータが先導する産学連携による材料開発〜リチウムイオン電池〜","館山 佳尚, 奥野幸洋, 古屋和彦","館山 佳尚, 奥野幸洋, 古屋和彦","スーパーコンピュータ推進議員連盟総会","スーパーコンピュータ推進議員連盟総会","2014-08-23","","jpn","oral_presentation","","","","","","","私たちは高精度計算が可能な第一原理分子動力学法と化学反応の自由エネルギー計算手法を融合させた計算技術を世界で初めてLIBに適用し、典型的な電解液内での還元分解過程とSEI膜の素材となる重合過程を原子・分子レベルで明らかにしました。発見した反応機構はいまだに謎が多いLIBの電解液分解と SEI膜形成過程の理解を増進するものとなっています。" "Additive effect on initial stage of solid electrolyte interphase (SEI) formation in lithium ion battery","Additive effect on initial stage of solid electrolyte interphase (SEI) formation in lithium ion battery","館山 佳尚","館山 佳尚","248th ACS National Meeting & Exposition","248th ACS National Meeting & Exposition","2014-08-10","","jpn","oral_presentation","","","","","","","Solid electrolyte interphase (SEI) formed through the reductive decomposition of electrolyte molecules plays a crucial role in the performance and stability of lithium-ion battery (LIB). Here we investigated the additive effects on the reductive decomposition, using a typical electrolyte system with ethylene carbonate (EC) solvent and vinylene carbonate (VC) additive." "DFT Simulation Study on Reactions in Electrolyte and at Electrode-Electrolyte Interface in Lithium Ion Battery","DFT Simulation Study on Reactions in Electrolyte and at Electrode-Electrolyte Interface in Lithium Ion Battery","館山 佳尚","館山 佳尚","The Eighth International Conference on the Science and Technolog","The Eighth International Conference on the Science and Technolog","2014-06-25","","jpn","oral_presentation","","","","","","","We carried out DFT-MD free energy calculations of the reductive decompositions of the carbonate-based electrolytes on the K computer, the flagship supercomputer in Japan, focusing on the thermodynamics as well as the kinetics. The reaction mechanisms in a novel type of superconcentrated electrolytes were examined with the same techniques as well. We then succeeded in theoretically elucidating, on the atomic scale, the reductive reaction mechanisms of the electrolyte molecules toward the SEI formation for the first time. Recently, we have also investigated the Li-ion behavior at oxide cathode/solid electrolyte interfaces and the effect of the buffer layers [3]. These new findings will contribute to the development of LIBs with higher performance, better safety and longer cycle life." "Acetonitrile Solution Effect on Ru N749 Dye Adsorption and Excitation at TiO2 Anatase Interface","Acetonitrile Solution Effect on Ru N749 Dye Adsorption and Excitation at TiO2 Anatase Interface","館山 佳尚, 大谷 優介, 児玉 小春, 韓 礼元, 袖山 慶太郎","館山 佳尚, 大谷 優介, 児玉 小春, 韓 礼元, 袖山 慶太郎","The 3rd Tsukuba Workshop on Organic Photovoltaics","The 3rd Tsukuba Workshop on Organic Photovoltaics","2014-06-03","","jpn","oral_presentation","","","","","","","Although the organic-inorganic hybrid perovskites have emerged as solar cells with higher efficiency, the interfacial chemistry of conventional Ru dyes at TiO2 - acetonitrile interfaces in dye-sensitized solar cells (DSCs) is still an issue of fundamental importance. We then investigated stable structures and photoexcitation character of Black Dye (BD; Ru N749 dye) adsorption to TiO2 anatase (101) interface immersed in bulk acetonitrile (AN) solution, a most representative DSC system. Density functional theory based molecular dynamics (DFT-MD) with explicit solvent molecules was used to take into account the fluctuations of solvation shells and adsorbed molecules. We have also combined time-dependent DFT calculations of the excitation energies and oscillator strengths for the discussion o" "「京」を用いた二次電池・太陽電池化学反応の第一原理MDシミュレーション","「京」を用いた二次電池・太陽電池化学反応の第一原理MDシミュレーション","館山 佳尚","館山 佳尚","次世代計算化学技術セミナー","次世代計算化学技術セミナー","2014-05-09","","jpn","oral_presentation","","","","","","","1:第一原理分子動力学法と酸化還元反応の記述 DFT-MDと酸化還元電位計算手法 2:LIB負極付近の電解液還元分解・重合の添加剤効果の解明 DFT-MDとBlue-moon ensemble 自由エネルギー法 3:LIB高機能電解液の還元耐性メカニズムの解明 DFT-MDと統計力学計算 4:LIB正極ー固体電解質界面の解析 DFT+U計算 5:DSC TiO2/Ru色素/電解液界面状態の解析 DFT-MDと線形応答TDDFT励起エネルギー計算 6:まとめ " "酸化物ー溶液界面の酸化還元反応の理論解析","酸化物ー溶液界面の酸化還元反応の理論解析","館山 佳尚","館山 佳尚","日本物理学会第69回年次大会","日本物理学会第69回年次大会","2014-03-27","","jpn","oral_presentation","","","","","","","我々のグループでは、触媒・電池の出口への展開を念頭に置きながら、各種酸化物ー溶液界面(TiO2/H2O, TiO2/色素/CH3CN, CeO2/H2O, LiCoO2界面など)の平衡状態・化学反応を、予言性の高いDFT-MDサンプリングを用いて解析し、一般的な原理の抽出に取り組んできた。本講演では、特に光触媒系のTiO2/H2O界面に焦点を当てながら、界面の酸化還元反応性の考察について紹介する。" "Theoretical study on structures and electronic states of boron-doped diamond (BDD) electrode/water interfaces","Theoretical study on structures and electronic states of boron-doped diamond (BDD) electrode/water interfaces","館山 佳尚, フテラ ズデニェク, 渡辺剛志, 栄長泰明","館山 佳尚, フテラ ズデニェク, 渡辺剛志, 栄長泰明","International Symposium on Diamond Electrochemistry","International Symposium on Diamond Electrochemistry","2014-03-18","","jpn","oral_presentation","","","","","","","In this work we have investigated the reactivity of BDD surfaces and interfaces based on their structural and electronic properties, by using DFT based computational techniques. Focusing on the (111) facet, we compare the electronic states between the BDD and un-doped diamond with different terminations (see Fig. 1 for H-terminated model). Performing calculations on these models we found that there are unoccupied surface state (SS) located in the upper part of the band gap on H-terminated surface, while on the surface covered by oxide or hydroxyl groups these states are in lower part of the gap close to valence band edge." "京で行う充電池材料開発〜スマホから電気自動車まで〜","京で行う充電池材料開発〜スマホから電気自動車まで〜","館山 佳尚","館山 佳尚","第2回TUT-CMSI見える化シンポジウム“電子を魅せる”","第2回TUT-CMSI見える化シンポジウム“電子を魅せる”","2014-03-08","","jpn","oral_presentation","","","","","","","私たちは高精度計算が可能な第一原理分子動力学法と化学反応の自由エネルギー計算手法を融合させた計算技術を世界で初めてLIBに適用し、典型的な電解液内での還元分解過程とSEI膜の素材となる重合過程を原子・分子レベルで明らかにしました。発見した反応機構はいまだに謎が多いLIBの電解液分解と SEI膜形成過程の理解を増進するものとなっています。 これらの計算は、一般のスーパーコンピュータでは実施が困難でしたが、京コンピュータを利用することにより短期間で素早く実行することができました。私たちの研究は、より高機能なSEI膜や高性能・高安全性をもたらす新しい電解液・添加剤の開発に対して京コンピュータ計算が十分貢献できることを示すものとなっています。 " "Novel mechanism of reductive decomposition of electrolyte in LIB: A DFT free energy analysis on K computer","Novel mechanism of reductive decomposition of electrolyte in LIB: A DFT free energy analysis on K computer","館山 佳尚","館山 佳尚","MANA International Symposium 2014","MANA International Symposium 2014","2014-03-05","","jpn","oral_presentation","","","","","","","Solid electrolyte interphase (SEI) on the electrode - electrolyte interfaces formed through the reductive decomposition of organic solvent molecules plays a crucial role in the stability and capability of lithium ion battery (LIB). Additives to the electrolyte often exhibit a large impact on the SEI quality. A typical example is vinylene carbonate (VC) additive to the ethylene carbonate (EC) solvent. Here we investigated the effects of VC additive to the EC solvent on the reductive decomposition and the initial stage of SEI formation. We focused on the thermodynamics as well as the kinetics of the possible processes. We used density functional theory based molecular dynamics (DFT-MD) with explicit solvent molecules for the equilibrium properties, and carried out the fre" "「京」で行う充電池材料開発〜スマホから電気自動車に向けて〜","「京」で行う充電池材料開発〜スマホから電気自動車に向けて〜","館山 佳尚","館山 佳尚","スーパーコンピュータ「京」を知る集いin熊本","スーパーコンピュータ「京」を知る集いin熊本","2014-02-15","","jpn","oral_presentation","","","","","","","「京」コンピュータを利用した充電池材料開発を一般の方々に分かりやすく説明しながら、スーパーコンピュータの必要性を広く知らしめる。" "Additive effect on reductive decomposition and binding of carbonate-based electrolyte in Lithium ion battery: A DFT free energy analysis","Additive effect on reductive decomposition and binding of carbonate-based electrolyte in Lithium ion battery: A DFT free energy analysis","館山 佳尚","館山 佳尚","TNTJapan2014","TNTJapan2014","2014-01-30","","jpn","oral_presentation","","","","","","","We focused on the thermodynamics as well as the kinetics of the possible processes. We used density functional theory based molecular dynamics (DFT-MD) with explicit solvent molecules for the equilibrium properties, and carried out the free energy profile calculations along the reaction pathways using the blue-moon ensemble technique. We compared between Li+ in only EC solvent (EC system) and in EC solvent with a VC additive (EC/VC system) to elucidate the additive effect. Nosé thermostat with a temperature of 353 K is adopted for the finite temperature effect. Further tuning of the DFT-MD code was made for the use of the ten-petaflops supercomputer (K computer) in Japan." "DFT-MD Analysis of Redox Reaction at Solid-Electrolyte Interface in Battery and Solar Cell","DFT-MD Analysis of Redox Reaction at Solid-Electrolyte Interface in Battery and Solar Cell","館山 佳尚","館山 佳尚","One Day Workshop on Chemical Reactions at Surfaces and Interface","One Day Workshop on Chemical Reactions at Surfaces and Interface","2014-01-20","","jpn","oral_presentation","","","","","","","In this talk, I" "京コンピュータ上での第一原理分子動力学計算を用いたリチウムイオン二次電池の電解液化学反応とSEI形成過程の微視的解析 ","京コンピュータ上での第一原理分子動力学計算を用いたリチウムイオン二次電池の電解液化学反応とSEI形成過程の微視的解析 ","館山 佳尚","館山 佳尚","日本化学会 電気化学ディビジョン  化学電池材料研究会 第33回講","日本化学会 電気化学ディビジョン  化学電池材料研究会 第33回講","2013-12-18","","jpn","oral_presentation","","","","","","","1:第一原理分子動力学法と酸化還元反応の記述 2:LIB負極付近の電解液還元分解・重合の添加剤効果について 3:最近の研究 A: グラファイト負極ーEC電解液界面のSEIの構造と性質、B: 電解液(溶媒、添加剤)・リチウム塩探索、C: 正極ー固体電解質界面の解析 " "TiO2ルチル・アナターゼ/水界面における光触媒反応性のDFT-MD解析","TiO2ルチル・アナターゼ/水界面における光触媒反応性のDFT-MD解析","館山 佳尚","館山 佳尚","第20回記念シンポジウム光触媒反応の最近の展開","第20回記念シンポジウム光触媒反応の最近の展開","2013-12-13","","jpn","oral_presentation","","","","","","","我々はこのTiO2界面における酸化還元・電子移動過程の理解と効率向上への指針探索を目標に、第一原理分子動力学計算を用いたTiO2/H2O界面の微視的状態に関する理論研究を行った。光触媒機能は湿潤環境下で大きく発現することから、特にバルクの水がTiO2面上に存在する場合に焦点をあてた。一般にアナターゼ型(101)面が他の面やルチル型表面よりも効率が良いと考えられていることを念頭に、その理由を探るべく、アナターゼ型(101)面および(001)面とルチル型(110)面などの比較にも取り組んだ。その結果、従来信じられているものとは異なる反応メカニズムがもっともらしいという結果を得た。" "A DFT-MD Analysis of Redox Reaction at Solid-Electrolyte Interface in Battery and Solar Cell","A DFT-MD Analysis of Redox Reaction at Solid-Electrolyte Interface in Battery and Solar Cell","館山 佳尚","館山 佳尚","5th JCS International Symposium on Theoretical Chemistry","5th JCS International Symposium on Theoretical Chemistry","2013-12-02","","jpn","oral_presentation","","","","","","","Solid electrolyte interphase (SEI) formed through the reductive decomposition of electrolyte molecules plays a crucial role in the performance and stability of lithium-ion battery (LIB). Here we investigated the additive effects on the reductive decomposition, using a typical electrolyte system with ethylene carbonate (EC) solvent and vinylene carbonate (VC) additive. We focused on both thermodynamics and kinetics of the possible processes, and used DFT molecular dynamics with explicit solvent as well as Blue-moon ensemble technique for the free energy change. " "DFT studies on adsorption and excitation of TiO2/Ru dye/CH3CN interfaces","DFT studies on adsorption and excitation of TiO2/Ru dye/CH3CN interfaces","館山 佳尚","館山 佳尚","International Conference on Dye-sensitized Solar Cell","International Conference on Dye-sensitized Solar Cell","2013-11-27","","jpn","oral_presentation","","","","","","","“deprotonated 2-anchor” modes are most stable for BD adsorption at TiO2 anatase/AN interface. But a certain amount of “protonated 1-anchor” is comparable. AN plays a crucial role of solvation, control of TiO2 & BD dipole, and adsorption stability. Regarding the NIR region absorption of BD, “protonated 1-anchor” seems more responsible. “Deprotonated 2-anchor” has larger driving force of electron injection. For theoretical discussion on the injection and back ET, “combination of TDDFT excitation & DFT PDOS” seems more relevant than the conventional DFT HOMO-LUMO argument." "「京」を用いたLIB電解液の還元分解から膜形成にいたる過程の反応解析","「京」を用いたLIB電解液の還元分解から膜形成にいたる過程の反応解析","館山 佳尚","館山 佳尚","第7回 CMSI産官学連続研究会","第7回 CMSI産官学連続研究会","2013-11-21","","jpn","oral_presentation","","","","","","","1:緒言:Lithium Ion Battery (LIB)、Solid Electrolyte Interphase (SEI)電解液(溶媒・添加剤)の還元分解 2:手法・計算:DFT-MD、卑電位モデル、Blue-Moon Ensemble、京コンピュータ 3:結果・考察:溶媒和、電子親和力、1電子還元、2電子還元、ラジカル攻撃 4:まとめ: " "Beta-Cyclodextrin-crosslinked alginate gel operated by mechanical stimuli: towards patient-controlled drug delivery systems","Beta-Cyclodextrin-crosslinked alginate gel operated by mechanical stimuli: towards patient-controlled drug delivery systems","KAWAKAMI, Kohsaku, IZAWA, Hironori, SUMITA, Masato, TATEYAMA, Yoshitaka, HILL, Jonathan, ARIGA, Katsuhiko","KAWAKAMI, Kohsaku, IZAWA, Hironori, SUMITA, Masato, TATEYAMA, Yoshitaka, HILL, Jonathan, ARIGA, Katsuhiko","AAPS Annual Meeting and Exposition 2013","AAPS Annual Meeting and Exposition 2013","2013-11-10","","eng","oral_presentation","","","","","","Although various drug delivery technologies have been developed, there are no current methods that enable ubiquitous dosage control by patients. Here we report a novel controlled release system with Cyclodextrin (CyD) -crosslinked alginate (AL), CCAL, composed of a CyD derivative junction point with AL as a main chain polymer, triggered by a mechanical stimulus generated by a patient’s hand. ","" "DFT-MD study of additive effects on reductive decomposition of carbonate-based solvent toward solid electrolyte interphase formation ","DFT-MD study of additive effects on reductive decomposition of carbonate-based solvent toward solid electrolyte interphase formation ","袖山 慶太郎, 後瀉 敬介, 奥野 幸洋, 館山 佳尚","袖山 慶太郎, 後瀉 敬介, 奥野 幸洋, 館山 佳尚","224th ECS Meeting","224th ECS Meeting","2013-10-27","","jpn","oral_presentation","","","","","","","We focused on the thermodynamics as well as the kinetics of the possible processes. We used density functional theory-based molecular dynamics (DFT-MD) with explicit solvent molecules at finite temperature for sampling of the equilibrium properties and carried out the free energy calculations of the reactions with the Blue-Moon Ensemble technique. We considered Li+ in only EC solvent (EC system) and in EC solvent with a VC additive (EC/VC system) to elucidate the additive effect. For the decomposition kinetics, we evaluated the free energy change along reaction pathways of EC or VC under one electron and two electron reduction conditions." "Lithium-air batteries: a DFT-MD study of the stability of Li+ + O2*– and LiO*– in DMSO and PC electrolytes","Lithium-air batteries: a DFT-MD study of the stability of Li+ + O2*– and LiO*– in DMSO and PC electrolytes","Johan Scheers, フテラ ズデニェク, 袖山 慶太郎, 館山 佳尚","Johan Scheers, フテラ ズデニェク, 袖山 慶太郎, 館山 佳尚","224th ECS Meeting","224th ECS Meeting","2013-10-27","","jpn","oral_presentation","","","","","","","Here we present the results from DFT-MD simulations of the radicals O2*– and LiO*– in PC and dimetylsulfoxide (DMSO) with the aim of identifying electrolyte properties that could be used to a priori address the compatibility of electrolyte solvents and oxygen reduction products in Li–O2 batteries." "DFT-MD Analysis of Redox Reaction at Solid-Electrolyte Interface in Battery and Solar Cell","DFT-MD Analysis of Redox Reaction at Solid-Electrolyte Interface in Battery and Solar Cell","館山 佳尚","館山 佳尚","16th Asian workshop on first-principles electronic structure cal","16th Asian workshop on first-principles electronic structure cal","2013-10-28","","jpn","oral_presentation","","","","","","","Redox reactions (electron transfer) at solid-liquid interfaces play crucial roles in diverse topics in energy and environmental issues, such as Lithium ion battery (LIB), dye-sensitized solar cell (DSSC), fuel cell and photocatalysis. Although many developments have been already made in these fields, the atomistic mechanisms have been still open questions.In this talk, I'll introduce our recent works on the LIB electrolytes [1] and the interfaces of DSSC [2-3]." "レア・イベントの理論科学:物性科学からの取り組み","レア・イベントの理論科学:物性科学からの取り組み","館山 佳尚","館山 佳尚","第1回レア・イベント理論科学ワークショップ","第1回レア・イベント理論科学ワークショップ","2013-10-23","","jpn","oral_presentation","","","","","","","電極界面のレア・イベントに対する第一原理統計力学理論 凝縮系光励起に関するレア・イベントの動的相関電子状態理論 構造変化に関するレア・イベントのサンプリング理論 " "酸化還元・固液界面反応計算手法開発と触媒・電池への応用 〜計算電気化学の構築に向けて〜","酸化還元・固液界面反応計算手法開発と触媒・電池への応用 〜計算電気化学の構築に向けて〜","館山 佳尚","館山 佳尚","応用化学科談話会","応用化学科談話会","2013-10-19","","jpn","oral_presentation","","","","","","","1:イントロ DFTと電気化学 2:酸化還元・電子移動反応の理論計算手法の開発・確立 3:固液界面計算手法+触媒・電池への応用例 " "第一原理分子動力学計算によるリチウムイオン二次電池電解液および添加剤のSEI形成反応解析","第一原理分子動力学計算によるリチウムイオン二次電池電解液および添加剤のSEI形成反応解析","奥野 幸洋, 後瀉 敬介, 袖山 慶太郎, 館山 佳尚","奥野 幸洋, 後瀉 敬介, 袖山 慶太郎, 館山 佳尚","第54回電池討論会","第54回電池討論会","2013-10-07","","jpn","oral_presentation","","","","","","","本研究では、顕に溶媒のダイナミクスを考慮した自由エネルギーに基づく平衡状態および反応自由エネルギー解析を行い、ECやVCの還元後の反応過程を明らかにし、SEI形成におけるVCの役割について知見を得ることを目的とした。" "第一原理分子動力学計算によるリチウムイオン二次電池電解液および添加剤のSEI形成反応解析","第一原理分子動力学計算によるリチウムイオン二次電池電解液および添加剤のSEI形成反応解析","後瀉 敬介, 袖山 慶太郎, 館山 佳尚, 奥野 幸洋","後瀉 敬介, 袖山 慶太郎, 館山 佳尚, 奥野 幸洋","2013年電気化学会季大会","2013年電気化学会季大会","2013-09-27","","jpn","oral_presentation","","","","","","","本研究では、顕に溶媒のダイナミクスを考慮した自由エネルギーに基づく平衡状態および反応自由エネルギー解析を行い、ECやVCの還元後の反応過程を明らかにし、SEI形成におけるVCの役割について知見を得ることを目的とした。" "DFT-MD自由エネルギー計算による リチウムイオン電池電解液・添加剤の還元反応解析","DFT-MD自由エネルギー計算による リチウムイオン電池電解液・添加剤の還元反応解析","館山 佳尚, 袖山 慶太郎, 後瀉 敬介, 奥野 幸洋","館山 佳尚, 袖山 慶太郎, 後瀉 敬介, 奥野 幸洋","第7回分子科学討論会2013","第7回分子科学討論会2013","2013-09-24","","jpn","oral_presentation","","","","","","","本研究では、顕に溶媒のダイナミクスを考慮した自由エネルギーに基づく平衡状態および反応自由エネルギー解析を行い、ECやVCの還元後の反応過程を明らかにし、SEI形成におけるVCの役割について知見を得ることを目的とした。" "CYCLODEXTRIN-CROSSLINKED ALGINATE GEL FOR MECHNICALLY-CONTROLLED DRUG DELIVERY SYSTEM ","CYCLODEXTRIN-CROSSLINKED ALGINATE GEL FOR MECHNICALLY-CONTROLLED DRUG DELIVERY SYSTEM ","KAWAKAMI, Kohsaku, IZAWA, Hironori, SUMITA, Masato, TATEYAMA, Yoshitaka, HILL, Jonathan, ARIGA, Katsuhiko","KAWAKAMI, Kohsaku, IZAWA, Hironori, SUMITA, Masato, TATEYAMA, Yoshitaka, HILL, Jonathan, ARIGA, Katsuhiko","3rd Conference on Innovation in Drug Delivery","3rd Conference on Innovation in Drug Delivery","2013-09-22","","eng","oral_presentation","","","","","","A mechanically-controlled drug delivery system with Cyclodextrin (CyD) -crosslinked alginate (AL), CCAL, composed of a CyD derivative junction point with AL as a main chain polymer, is introduced.","" "第一原理MDによるボロンドープダイヤモンド電極/水溶液界面の電子状態と反応性解析A","第一原理MDによるボロンドープダイヤモンド電極/水溶液界面の電子状態と反応性解析","館山 佳尚, フテラ ズデニェク, 渡辺剛志, 栄長泰明","館山 佳尚, フテラ ズデニェク, 渡辺剛志, 栄長泰明","第112回触媒討論会","第112回触媒討論会","2013-09-18","","jpn","oral_presentation","","","","","","","化学的安定性と電気伝導性を兼ね備えたボロンドープダイヤモンドは水質浄化等に向けた新規な電極触媒として着目されている。本研究では、動作環境下におけるボロンドープダイヤモンド/水界面の電子状態や反応性について、第一原理分子動力学(MD)シミュレーションを実行し、その微視的メカニズムの解明を試みた。その結果は炭素電極一般に関する知見も与えるものとなっている。" "DFT+U Study of Cu/CeO2 Model Catalysts","DFT+U Study of Cu/CeO2 Model Catalysts","サボバ ルチエ, Oleksander Stetsovych, Filip Dvorak, Matteo F. Camellone, Josef Myslivecek, Vladimir Matolin, Stefano Fabris, 館山 佳尚","サボバ ルチエ, Oleksander Stetsovych, Filip Dvorak, Matteo F. Camellone, Josef Myslivecek, Vladimir Matolin, Stefano Fabris, 館山 佳尚","2013 JSAP-MRS Joint Symposium","2013 JSAP-MRS Joint Symposium","2013-09-16","","jpn","oral_presentation","","","","","","","Environmental protection requires search for new, more effective and cheaper catalysts for reducing the air pollution as well as producing energy by a more environment-friendly methods. The heterogeneous catalysts are often composed of metal-oxides doped by metal nanostructures [1-3]. The choice of both metal and substrate is substantial for properties of the catalyst. Reducible oxides such as ceria are known to show a particular ability to activate supported metal clusters. We investigated thermodynamic, structural and electronic properties of copper-ceria (CeO2) surfaces and interfaces. " "Investigation of Electronic States of Boron-Doped Diamond Surfaces by DFT","Investigation of Electronic States of Boron-Doped Diamond Surfaces by DFT","フテラ ズデニェク, 栄長泰明, 館山 佳尚","フテラ ズデニェク, 栄長泰明, 館山 佳尚","2013 JSAP-MRS Joint Symposium","2013 JSAP-MRS Joint Symposium","2013-09-16","","jpn","oral_presentation","","","","","","","In this work we are presenting electronic states of BDD calculated under several different conditions. We explored B doping effect, surface termination effect and water interface structure." "Redox Reaction Mechanisms at TiO2 - Water Interfaces: A DFT Molecular Dynamics Study","Redox Reaction Mechanisms at TiO2 - Water Interfaces: A DFT Molecular Dynamics Study","館山 佳尚, 相川小春","館山 佳尚, 相川小春","64th Annual Meeting of the Internat. Society of Electrochemistry","64th Annual Meeting of the Internat. Society of Electrochemistry","2013-09-08","","jpn","oral_presentation","","","","","","","In this work, we focus on the TiO2 - water interfaces for typical photocatalyst models, and explore possible interfacial structures, electronic states and oxygen reduction reaction (ORR) processes, by using density functional theory based molecular dynamics (DFT-MD) simulations with explicit solvent and surface atoms." "Car-Parrinello MD and blue-moon ensemble study on reductive decomposition of carbonate-based solvent in lithium ion battery","Car-Parrinello MD and blue-moon ensemble study on reductive decomposition of carbonate-based solvent in lithium ion battery","館山 佳尚, 後瀉 敬介, 袖山 慶太郎, 奥野幸洋","館山 佳尚, 後瀉 敬介, 袖山 慶太郎, 奥野幸洋","CPMD2013","CPMD2013","2013-09-02","","jpn","oral_presentation","","","","","","","Solid electrolyte interphase (SEI) on the electrode - electrolyte interfaces formed through the reductive decomposition of organic solvent molecules plays a crucial role in the stability and capability of lithium ion battery (LIB). Additives to the electrolyte often exhibit a large impact on the SEI quality. A typical example is vinylene carbonate (VC) additive to the ethylene carbonate (EC) solvent (See Figure). Here we investigated the effects of VC additive to the EC solvent on the reductive decomposition and the initial stage of SEI formation. We focused on the thermodynamics as well as the kinetics of the possible processes. We used DFT-based Car-Parrinello MD with explicit solvent molecules for the equilibrium properties, and carried out the free energy profile calculation." "DFT investigation of electronic states and reactivity of boron-doped diamond – water interface","DFT investigation of electronic states and reactivity of boron-doped diamond – water interface","フテラ ズデニェク, 栄長泰明, 館山 佳尚","フテラ ズデニェク, 栄長泰明, 館山 佳尚","International Conference on Diamond and Carbon Materials 2013","International Conference on Diamond and Carbon Materials 2013","2013-09-02","","jpn","oral_presentation","","","","","","","In this work we have investigated the reactivity of BDD surfaces and interfaces based on their structural and electronic properties, by using DFT based computational techniques. Focusing on the (111) facet, we compare the electronic states between the BDD and un-doped diamond with different terminations (see Fig. 1 for H-terminated model). Performing calculations on these models we found that there are unoccupied surface state (SS) located in the upper part of the band gap on H-terminated surface, while on the surface covered by oxide or hydroxyl groups these states are in lower part of the gap close to valence band edge. " "エネルギー問題に対する計算物質科学","エネルギー問題に対する計算物質科学","館山 佳尚","館山 佳尚","CMSI 第1部会「新物質・新量子相の基礎科学」 夏の学校 2013","CMSI 第1部会「新物質・新量子相の基礎科学」 夏の学校 2013","2013-08-12","","jpn","oral_presentation","","","","","","","+酸化還元・電子移動反応の第一原理自由エネルギー計算(基礎) +エネルギー・環境問題に関連する固液界面現象の第一原理分子動力学解析(応用) " "Hydrogen-Enhanced Vacancy Embrittlement of Grain Boundaries in Iron: First-Principles Calculations","Hydrogen-Enhanced Vacancy Embrittlement of Grain Boundaries in Iron: First-Principles Calculations","籾田浩義, 浅利裕介, 中村 美道, 館山 佳尚, 大野 隆央","籾田浩義, 浅利裕介, 中村 美道, 館山 佳尚, 大野 隆央","ISAM4-2013","ISAM4-2013","2013-07-22","","jpn","oral_presentation","","","","","","","We have investigated vacancy-related mechanism that reduces grain-boundary strengths which are enhanced by hydrogen. Calculated results show that hydrogen stabilizes vacancies at grain boundaries, and the defects reduce the local tensile strengths of the grain boundaries. This deleterious effect is much worse than when interstitial hydrogen is trapped at grain boundaries without vacancies. Atomistic fracture behaviors associated with electronic bond breakings under static tensile loads can explain characters of the strength changes induced by the defects. The vacancy-related hydrogen embrittlement mechanism may account for slowly developing damage inside a material due to the slow mobility of vacancies." "DFT-MD study on TiO2/solution interfaces under equilibrium in photocatalysis and dye-sensitised solar cell","DFT-MD study on TiO2/solution interfaces under equilibrium in photocatalysis and dye-sensitised solar cell","館山 佳尚","館山 佳尚","HAYASHI CONFERENCE","HAYASHI CONFERENCE","2013-07-16","","jpn","oral_presentation","","","","","","","We have been exploring possible interfacial structures and electronic states of TiO2/liquid water interfaces for PC and TiO2/liquid acetonitrile for DSC under thermal equilibrium, by using density functional theory based molecular dynamics (DFTMD) analysis with the explicit solvent molecules. Recently, we have also addressed to analyze the redox reaction ability at the PC interfaces as well as a role of redox mediators in the DSSC systems, with some novel computational techniques." "患者自身が押す力で薬物放出を制御するインプラント型ゲル製剤","患者自身が押す力で薬物放出を制御するインプラント型ゲル製剤","川上 亘作, 井澤 浩則, 隅田 真人, 館山 佳尚, ヒル ジョナサン, 有賀 克彦","川上 亘作, 井澤 浩則, 隅田 真人, 館山 佳尚, ヒル ジョナサン, 有賀 克彦","第29回日本DDS学会","第29回日本DDS学会","2013-07-04","","jpn","oral_presentation","","","","","","","光・磁場・熱などの外部刺激に反応して薬物を放出する担体は広く検討されているが、これらの利用には特殊機器が必要となる。本研究では、患者自身が手で与えるマクロな力でホストーゲスト相互作用を制御し、薬物投与を行うDDSを提案する。" "アナターゼTiO2(101)表面に吸着したアセトニトリル分子の電子状態","アナターゼTiO2(101)表面に吸着したアセトニトリル分子の電子状態","隅田 真人, 袖山 慶太郎, 城野亮太, 館山 佳尚","隅田 真人, 袖山 慶太郎, 城野亮太, 館山 佳尚","物性研究所共同利用スパコン合同研究会「計算物性物理学の新展開」","物性研究所共同利用スパコン合同研究会「計算物性物理学の新展開」","2013-01-10","","jpn","oral_presentation","","","","","","","アナターゼTiO2 (101)/アセトニトリル (MeCN) 溶媒の界面は色素増感太陽電池(DSSC)の化学的メカニズムを理解する上で重要な系である.ここでは,アナターゼTiO2 (101)表面に吸着したMeCN一分子の詳細な電子状態を,ハイブリッド交換相関関数を用いた密度汎関数法で解析した.この結果によるとMeCNの7a1軌道が吸着によってもっとも大きく変化している軌道であり,NA(MeCNの窒素原子)の直下であるTi5C (五配位のTi)では無く,O3C (三配位O)と結合性軌道を形成している.この吸着MeCNの電子状態はMeCNの吸着構造と被覆率に大きく関わっていると思われる. " "固液界面の酸化還元過程に関する第一原理計算解析","固液界面の酸化還元過程に関する第一原理計算解析","館山 佳尚","館山 佳尚","表面科学学術講演会","表面科学学術講演会","2012-11-20","","jpn","oral_presentation","","","","","","","近年、(光)触媒、(太陽・燃料・二次)電池の研究が精力的に進められているが、エネルギー生成や分解・合成反応の主要な場である固液界面の原子・電子スケールでの理解はまだ確立したとは言いがたい。このような問題に対して量子力学理論をベースとした計算(DFT計算)を用いて理解を進めようという試みが最近出始めてきている。しかしながら、量子力学的描像と長い歴史を持つ電気化学的概念にはまだズレが存在し統一的な理解には至っていない。そこで私たちはDFT分子動力学(MD)法による酸化還元過程の定量的な取扱いの確立を通して、この不一致を解消しようと取り組んでいる。その実証系として調べた TiO2電極界面が含まれる光触媒系・色素増感太陽電池系の第一原理計算解析について報告する。" "Development of cyclodextrin-based functional polymeric excipients towards patient-friendly drug delivery systems","Development of cyclodextrin-based functional polymeric excipients towards patient-friendly drug delivery systems","川上 亘作, 井澤 浩則, 大門 裕貴, 隅田 真人, 館山 佳尚, 酒井秀樹, 阿部正彦, ヒル ジョナサン, 有賀 克彦","川上 亘作, 井澤 浩則, 大門 裕貴, 隅田 真人, 館山 佳尚, 酒井秀樹, 阿部正彦, ヒル ジョナサン, 有賀 克彦","10th Japan-Korea Symposium on Materials & Interface","10th Japan-Korea Symposium on Materials & Interface","2012-11-07","","jpn","oral_presentation","","","","","","","Drug molecules can be delivered into human bodies via various routes. Although the oral administration is the most convenient route, other routes are also employed depending on characteristics of drug molecules and diseases. Friendliness to patients is one of the important factors for establishing the administration methodology, because it may significantly influence patient’s compliance. In this presentation, our attempts to develop novel functional polymers that can be used for patient-friendly drug delivery systems." "第一原理計算によるTiO2/H2O界面の原子スケール解析","第一原理計算によるTiO2/H2O界面の原子スケール解析","館山 佳尚","館山 佳尚","第110回触媒討論会","第110回触媒討論会","2012-09-24","","jpn","oral_presentation","","","","","","","第一原理DFT分子動力学(MD)サンプリングを用いて、光触媒系TiO2 /水界面の室温平衡下における構造および電子的性質を原子・電子スケールから明らかにした。アナターゼ型構造の表面に対し、バルク水の存在下における表面欠陥・再構成の安定性、表面への水分子吸着および界面における水素結合様式について微視的知見を得た。さらに反応理解の鍵となる電子状態の解析も行った。" "色素増感太陽電池電極アナターゼTiO2 (101)/ アセトニトリル界面における水分子の影響 ","色素増感太陽電池電極アナターゼTiO2 (101)/ アセトニトリル界面における水分子の影響 ","隅田 真人, 袖山 慶太郎, 館山 佳尚","隅田 真人, 袖山 慶太郎, 館山 佳尚","日本物理学会秋季大会","日本物理学会秋季大会","2012-09-18","","jpn","oral_presentation","","","","","","","本研究では,アナターゼナノ粒子で最も大面積を占める(101)面/MeCN 界面に混入した水分子の影響を、DFT分子動力学計算を用いた構造・電子状態サンプリングを用いて調べた。" "Water contamination effect on liquid acetonitrile / TiO2 anatase (101) interface for durable dye-sensitized solar cell","色素増感太陽電池電極アナターゼTiO2 (101)/アセトニトリル界面における水分子の影響","隅田 真人, 袖山 慶太郎, 館山 佳尚","隅田 真人, 袖山 慶太郎, 館山 佳尚","第6回分子科学討論会","第6回分子科学討論会","2012-09-18","","jpn","oral_presentation","","","","","","","ナターゼTiO2とアセトニトリル(MeCN)界面は色素増感太陽電池(DSSC)の陰極における重要な系である.DSSCは大気下で作成されるため水分子の混入を防ぐ事は困難であると考えられる.従って,混入した水分子の効果を考慮することは重要である.本研究では,第一原理分子動力学法を用いてTiO2/液体MeCN界面付近の水分子の構造と電子状態を解析し,どのような条件下でDSSCを作る事が望ましいかを報告する." "TiO2/水界面の電子・正孔状態に関する第一原理計算解析","TiO2/水界面の電子・正孔状態に関する第一原理計算解析","館山 佳尚","館山 佳尚","ISSPワークショップ表面・界面における輸送と変換","ISSPワークショップ表面・界面における輸送と変換","2012-07-13","","jpn","oral_presentation","","","","","","","1: 光触媒系(主にTiO2系)に対するDFT計算アプローチの現状2: Anatase/Rutile TiO2/’bulk’ water interfaceの構造・電子状態3: Anatase TiO2/’bulk’ water interfaceの酸素還元反応4: Summary & Future " "DFT approaches to semiconductor/oxide-solution interfaces","DFT approaches to semiconductor/oxide-solution interfaces","館山 佳尚","館山 佳尚","MASP2012","MASP2012","2012-06-25","","jpn","oral_presentation","","","","","","","半導体・酸化物電極/溶液界面に対する第一原理MDシミュレーション解析の最新研究について講義する。" "第一原理計算によるTiO2/H2O界面の原子スケール解析","第一原理計算によるTiO2/H2O界面の原子スケール解析","館山 佳尚","館山 佳尚","第12回光触媒研究討論会","第12回光触媒研究討論会","2012-07-10","","jpn","oral_presentation","","","","","","","理論計算の立場から界面酸化還元反応メカニズム解明し、触媒研究の技術的ブレークスルーに貢献 " "患者自身が与える機械的刺激で薬物放出を制御するインプラントゲルの開発","患者自身が与える機械的刺激で薬物放出を制御するインプラントゲルの開発","川上 亘作, 井澤 浩則, 隅田 真人, 館山 佳尚, ヒル ジョナサン, 有賀 克彦","川上 亘作, 井澤 浩則, 隅田 真人, 館山 佳尚, ヒル ジョナサン, 有賀 克彦","第28回日本DDS学会","第28回日本DDS学会","2012-07-04","","jpn","oral_presentation","","","","","","","押したり引っ張ったりという単純な機械力で分子レベルの相互作用を制御する研究が注目されており、この原理を利用すれば、患者自身の物理的な力で、薬物放出を制御する担体が開発できるかもしれない。我々は第一原理分子動力学シミュレーションより、シクロデキストリン(CyD)が圧力変化で僅かに変形することを見出した。これは、機械刺激によってCyDと薬物の相互作用が制御できる可能性を示している。そこでアルギン酸カルシウムネットワークに-CyDを含むゲルを合成し、CyD部位に制吐剤のオンダンセトロンを包摂させ、リン酸緩衝液中で指圧を想定した加圧を行ったところ、加圧に応じた継続的な薬物放出が観察された。以上の検討より、指圧のような単純な機械力で薬物放出を制御できるインプラントゲルが創製できる可能性が示唆された。" "DFT-MD Analysis of Interfacial Charge Transfer at TiO2/ Solution Interfaces for Photocatalysis and Solar Cell","DFT-MD Analysis of Interfacial Charge Transfer at TiO2/ Solution Interfaces for Photocatalysis and Solar Cell","館山 佳尚, 隅田 真人, 袖山 慶太郎","館山 佳尚, 隅田 真人, 袖山 慶太郎","Spring meeting of international society of electrochemistry","Spring meeting of international society of electrochemistry","2012-05-23","","jpn","oral_presentation","","","","","","","we explore possible interfacial structures and electronic states of TiO2/liquid water interfaces for PC and TiO2/liquid acetonitrile for DSC under thermal equilibrium, by using density functional theory based molecular dynamics (DFTMD) analysis. With the averaged electronic states and the view of semiconductor junctions involving electric double and space-charge layers, we discuss possible pathways of the charge transfer processes. " "機械的刺激を用いる新規ドラッグデリバリースステム","機械的刺激を用いる新規ドラッグデリバリースステム","井澤 浩則, 川上 亘作, 隅田 真人, 館山 佳尚, ヒル ジョナサン, 有賀 克彦","井澤 浩則, 川上 亘作, 隅田 真人, 館山 佳尚, ヒル ジョナサン, 有賀 克彦","日本化学会第92春季年会(2012) ","日本化学会第92春季年会(2012) ","2012-03-25","","jpn","oral_presentation","","","","","","","誰もが、いついかなる時でも発生させることができる機械的刺激を用いて薬物の放出制御ができれば、患者自身が症状に合わせて自由に薬物を摂取できる新たなインプラント型のドラッグデリバリーシステムの構築につながる。本研究では、シクロデキストリンを分子ネットワークに含むヒドロゲルを用いることで、機械的刺激による薬物の放出制御に成功した。" "色素増感太陽電池における固液界面に吸着した遷移金属錯体色素の光吸収スペクトル解析","色素増感太陽電池における固液界面に吸着した遷移金属錯体色素の光吸収スペクトル解析","館山 佳尚, 隅田 真人, 袖山 慶太郎","館山 佳尚, 隅田 真人, 袖山 慶太郎","ナノライフ公開シンポジウム","ナノライフ公開シンポジウム","2012-03-05","","jpn","oral_presentation","","","","","","","我々はTiO2/色素/電解質溶液系への展開を念頭に、高変換効率をもたらすRuピリジル色素に着目し、そのTiO2アナターゼ(101)表面への吸着状態に関する理論解析に取り組んだ。" "酸化還元反応・固液界面のDFT-MD理論解析","酸化還元反応・固液界面のDFT-MD理論解析","館山 佳尚","館山 佳尚","東京大学応用化学談話会","東京大学応用化学談話会","2012-03-03","","jpn","oral_presentation","","","","","","","我々が最近取り組んでいるTiO2/H2O界面系の酸化還元反応のDFT-MD理論解析について説明する。" "Water Contamination Effect on Liquid Acetonitrile / TiO2 Anatase (101) Interface for Durable Dye-sensitized Solar Cell","Water Contamination Effect on Liquid Acetonitrile / TiO2 Anatase (101) Interface for Durable Dye-sensitized Solar Cell","隅田 真人, 袖山 慶太郎, 韓 礼元, 館山 佳尚","隅田 真人, 袖山 慶太郎, 韓 礼元, 館山 佳尚","MANA International Symposium 2012","MANA International Symposium 2012","2012-02-29","","jpn","oral_presentation","","","","","","","We report structural and electronic properties of liquid acetonitrile (MeCN) / TiO2 anatase (101) interfaces involving a water molecule in order to analyze effect of ubiquitous water contamination in the typical electrolyte solution on the durability of dye-sensitized solar cell (DSSC), by using density-functional molecular dynamics simulations at room temperature. " "First-Principles Study on Semiconductor / Liquid Interfaces for Energy and Environmental issues","First-Principles Study on Semiconductor / Liquid Interfaces for Energy and Environmental issues","館山 佳尚","館山 佳尚","The 3rd GREEN symposium","The 3rd GREEN symposium","2012-02-27","","jpn","oral_presentation","","","","","","","For the last years, we have explored possible interfacial structures and electronic states of TiO2/liquid water interfaces for PC and TiO2/liquid acetonitrile for DSC under thermal equilibrium, by using density functional theory based molecular dynamics (DFTMD) analysis. With the averaged electronic states and the view of semiconductor junctions involving electric double and space-charge layers, we have discussed possible pathways of the charge transfer processes." "光触媒・太陽電池系TiO2/溶液界面の第一原理MD解析","光触媒・太陽電池系TiO2/溶液界面の第一原理MD解析","隅田 真人, 袖山 慶太郎, 館山 佳尚","隅田 真人, 袖山 慶太郎, 館山 佳尚","「連携ラボ」第7回公開シンポジウム","「連携ラボ」第7回公開シンポジウム","2012-02-23","","jpn","oral_presentation","","","","","","","TiO2/液体界面の原子ベルの解析は,光触媒や太陽電池設計に重要である.本発表では,TiO2/水,TiO2/アセトニトリル界面について,第一原理計算による成果を発表した." "色素増感太陽電池系電極/電解質溶液界面・Ru色素吸着に関する第一原理計算解析","色素増感太陽電池系電極/電解質溶液界面・Ru色素吸着に関する第一原理計算解析","館山 佳尚, 隅田 真人, 袖山 慶太郎","館山 佳尚, 隅田 真人, 袖山 慶太郎","第2回計算物質科学イニシアティブ(CMSI)研究会","第2回計算物質科学イニシアティブ(CMSI)研究会","2012-01-30","","jpn","oral_presentation","","","","","","","本研究では,アナターゼナノ粒子で最も大面積を占める(101)面/MeCN 界面に混入した水分子の影響を,第一原理密 度汎関数法分子動力学計算を用いて調べた." "光触媒TiO2/水界面の吸着水・水素結合・化学反応性の理論計算","光触媒TiO2/水界面の吸着水・水素結合・化学反応性の理論計算","館山 佳尚","館山 佳尚","JST「ナノ界面の基盤技術の構築」領域第1回公開ワークショップ","JST「ナノ界面の基盤技術の構築」領域第1回公開ワークショップ","2012-01-25","","jpn","oral_presentation","","","","","","","私は密度汎関数理論(DFT)と分子動力学(MD)サンプリングを組み合わせた固液界面系の理論的探索手法の開発・確立に従事してきました。この方向性は従来用いられてきた静的なDFT計算や経験ポテンシャルMDと一線を画すものとなっており、新規なアプローチとなっています。この固液界面解析の一環として、代表的な光触媒系でありかつ基礎的にも重要なTiO2/水界面の原子・電子スケールでの熱平衡状態解析を行いました。特に効率が高いとされるTiO2 アナターゼ系に着目し、水に浸された(101)面および(001)面の熱平衡状態下での吸着水、界面水素結合および電子状態について解析を行いました。本講演ではそれらの結果と界面化学反応に対する考察について報告します。" "TiO2/溶液界面の界面構造・電子状態:光触媒・色素増感太陽電池の微視的機構解明に向けて","TiO2/溶液界面の界面構造・電子状態:光触媒・色素増感太陽電池の微視的機構解明に向けて","館山 佳尚","館山 佳尚","物性科学WG・分子科学WG合同研究会 燃料電池 No.5","物性科学WG・分子科学WG合同研究会 燃料電池 No.5","2011-12-26","","jpn","oral_presentation","","","","","","","光触媒・色素増感太陽電池の微視的機構解明に向けて、TiO2/溶液界面の界面構造・電子状態を第一原理MDにより解析した。" "Equilibrium Structures and Electronic States of TiO2/Solution Interfaces for Dye-Sensitized Solar Cell and Photocatalysis: DFT-MD Sampling Analysis","Equilibrium Structures and Electronic States of TiO2/Solution Interfaces for Dye-Sensitized Solar Cell and Photocatalysis: DFT-MD Sampling Analysis","館山 佳尚","館山 佳尚","21st Academic Symposium of MRS-Japan 2011","21st Academic Symposium of MRS-Japan 2011","2011-12-19","","jpn","oral_presentation","","","","","","","Atomistic mechanisms of chemical reactions at the TiO2/liquid interfaces of dye-sensitized solar cell (DSC) and photocatalysis (PC) have not yet been fully understood due to the experimental and computational difficulty in analyzing such buried interfaces. To solve these problems, we have been exploring density functional theory based molecular dynamics (DFTMD) sampling analysis of interfacial structures and electronic states under thermal equilibrium, on the atomic and electronic scales." "色素増感太陽電池電極アナターゼTiO2 (101)/アセトニトリル界面に おける水分子の影響","色素増感太陽電池電極アナターゼTiO2 (101)/アセトニトリル界面に おける水分子の影響","隅田 真人, 袖山 慶太郎, 館山 佳尚","隅田 真人, 袖山 慶太郎, 館山 佳尚","第31回 表面科学 学術講演会","第31回 表面科学 学術講演会","2011-12-15","","jpn","oral_presentation","","","","","","","アナターゼナノ粒子で最も大面積を占める(101)面/MeCN 界面に混入した水分子の影響を,第一原理密 度汎関数法分子動力学計算を用いて調べた結果を発表する." "TiO2/H2O界面のナノ構造・吸着水・界面水素結合および電子状態","TiO2/H2O界面のナノ構造・吸着水・界面水素結合および電子状態","館山 佳尚, 隅田 真人","館山 佳尚, 隅田 真人","第31回表面科学学術講演会","第31回表面科学学術講演会","2011-12-15","","jpn","oral_presentation","","","","","","","最も代表的な光触媒系であるTiO2 アナターゼ系はすでに多くの研究例・応用例があるものの、水溶液との界面における原子スケールの反応―水・有機分子分解(酸化)など―メカニズムは未だに良く分かっていない。この問題を明らかにするため、我々は第一原理分子動力学(MD)を用いた固液界面の平衡構造および平衡電子状態の解析に取り組んできた。本講演ではTiO2 アナターゼ(101)及び(001)/水界面の平衡状態下での吸着水・界面水素結合を中心に電子状態についても報告する。" "Dynamics of Nanoelectrochemistry","Dynamics of Nanoelectrochemistry","青野 正和, 長谷川 剛, 寺部 一弥, 鶴岡 徹, 大野 武雄, 日野 貴美, ナヤク アルパナ, 呉 守明, 大川 祐司, 館山 佳尚, マンダル スワパン クマー, 中山 知信, 中谷 真人","青野 正和, 長谷川 剛, 寺部 一弥, 鶴岡 徹, 大野 武雄, 日野 貴美, ナヤク アルパナ, 呉 守明, 大川 祐司, 館山 佳尚, マンダル スワパン クマー, 中山 知信, 中谷 真人","ISSS-6","ISSS-6","2011-12-11","","jpn","oral_presentation","","","","","",""," ナノスケールでの化学反応のダイナミクスとそれを制御するテクノロジーについて解説する。" "固液界面反応に向けた第一原理計算解析:色素増感太陽電池を中心に","固液界面反応に向けた第一原理計算解析:色素増感太陽電池を中心に","館山 佳尚","館山 佳尚","物性研短期研究会「エネルギー変換の物性科学」","物性研短期研究会「エネルギー変換の物性科学」","2011-11-14","","jpn","oral_presentation","","","","","","","色素増感太陽電池の微視的メカニズム解明を目的に、その代表的系であるTiO2/アセトニトリル界面、TiO2-black dye吸着系について第一原理MDおよびTDDFTを用いて行った研究内容を報告する。 " "非水溶媒/遷移金属酸化物界面の平衡構造・電子状態:第一原理MD解析","非水溶媒/遷移金属酸化物界面の平衡構造・電子状態:第一原理MD解析","館山 佳尚","館山 佳尚","CMSI 元素戦略WG 「電池材料の部」 実験計算連携検討会","CMSI 元素戦略WG 「電池材料の部」 実験計算連携検討会","2011-11-09","","jpn","oral_presentation","","","","","","","非水溶媒/金属酸化物の1例である、色素増感太陽電池のTiO2/アセトニトリル界面について、第一原理MDを適用して行った定常状態解析について報告する" "Protonated carboxyl anchor for stable adsorption of N749 Ru dye (black dye) on TiO2 anatase (101) surface","二酸化チタンアナターゼ(101)表面におけるN749ルテニウム色素(ブラックダイ)の吸着構造:プロトンを有するカルボキシル基による吸着","袖山 慶太郎, 隅田 真人, 館山 佳尚","袖山 慶太郎, 隅田 真人, 館山 佳尚","The 14th ASIAN Workshop","The 14th ASIAN Workshop","2011-10-31","","jpn","oral_presentation","","","","","","","本発表では二酸化チタンアナターゼ(101)表面に吸着するブラックダイの吸着構造および励起状態に関して第一原理計算による理論的検討を行った。考え得る4種類の吸着構造を計算により求めた結果、色素のカルボキシル基と表面のチタン原子との結合が1本である構造の方が2本の場合よりも安定であることを明らかにした。これは主に、結合が1本の場合には色素が自由に回転できるために色素と表面の間に水素結合ができることによる。また色素にプロトンが残ったままの構造の方が表面にプロトンが移動した場合よりも安定であることも明らかにした。その構造における励起状態計算を行ったところ、UV-visスペクトルが実験値とよい相関を示した。プロトンの存在する位置により太陽電池の効率は大きく変化すると言われており、本構造は新しい設計メカニズムに対する新しいコンセプトを提案している。" "First-Principles Study on Semiconductor Electrode/Liquid Interfaces for Photocatalysis and Dye-Sensitised Solar Cell ","First-Principles Study on Semiconductor Electrode/Liquid Interfaces for Photocatalysis and Dye-Sensitised Solar Cell ","館山 佳尚, 隅田 真人, 袖山 慶太郎","館山 佳尚, 隅田 真人, 袖山 慶太郎","Intl Sympo on Atomically Controlled Fabrication Technology","Intl Sympo on Atomically Controlled Fabrication Technology","2011-10-31","","jpn","oral_presentation","","","","","","","Though a lot of progress has been made in the development of photocatalysis and solar cell, atomistic mechanisms of the chemical reactions at the solid/liquid interfaces have not yet been fully understood because of the difficulty in analyzing such interfacial processes. In order to solve this problem, we have been studying semiconductor electrode/liquid interfaces, associated with photocatalysis (PC) and dye-sensitised solar cell (DSC), on the atomic and electronic scales, by use of quantitative theoretical simulations based on the density functional theory (DFT) with supercomputers." "Water Contamination Effect on Liquid Acetonitrile / TiO2 Anatase (101) Interface for Durable Dye-sensitized Solar Cell ","Water Contamination Effect on Liquid Acetonitrile / TiO2 Anatase (101) Interface for Durable Dye-sensitized Solar Cell ","隅田 真人, 袖山 慶太郎, 韓 礼元, 館山 佳尚","隅田 真人, 袖山 慶太郎, 韓 礼元, 館山 佳尚","The 14th Asian Workshop on First-Principles Electronic Structure","The 14th Asian Workshop on First-Principles Electronic Structure","2011-10-31","","jpn","oral_presentation","","","","","","","We have investigated structural and electronic properties of liquid acetonitrile (MeCN) / TiO2 anatase (101) interfaces involving a water molecule in order to analyze effect of ubiquitous water contamination in the typical electrolyte solution on the durability of dye-sensitized solar cell (DSSC), by using density-functional molecular dynamics simulations at room temperature." "Adsorption and photoexcitation of black dye (N749 Ru dye) on TiO2 anatase (101) surface for dye-sensitised solar cell ","Adsorption and photoexcitation of black dye (N749 Ru dye) on TiO2 anatase (101) surface for dye-sensitised solar cell ","館山 佳尚, 袖山 慶太郎, 隅田 真人","館山 佳尚, 袖山 慶太郎, 隅田 真人","ICTP-SISSA Workshop on New Materials for Renewable Energy","ICTP-SISSA Workshop on New Materials for Renewable Energy","2011-10-17","","jpn","oral_presentation","","","","","","","We have investigated adsorption and photoexication of another Ru-complex, black dye having a terpyridine ligand (Ru(4,4" "DFT spin-contamination problem on magnetic impurity defect in diamond","ダイヤモンド中磁性不純物欠陥の安定性に関するDFTスピン汚染問題","館山 佳尚, 大塚教雄, 原田慈久, 森田将史","館山 佳尚, 大塚教雄, 原田慈久, 森田将史","日本物理学会秋季大会2011","日本物理学会秋季大会2011","2011-09-21","","jpn","oral_presentation","","","","","","","Quantum computingや磁力計等への応用を目指し、diamond NV- centreの研究が現在盛んに行われている。我々は更なる高磁性・高安定性を目指してdiamond中にMn原子を埋め込んだ材料開発とその特性評価に取り組んでいる。本講演ではその磁性不純物欠陥の構造・スピン安定性に関するDFT計算解析、およびそこで直面したスピン汚染問題について報告する。" "Adsorption and excitation of Ru(II) polypyridyl complex on TiO2 anatase (101) surface for dye-sensitized solar cells","色素増感太陽電池におけるRu(II)ポリピリジル錯体のTiO2アナターゼ(101)表面吸着構造および励起状態に関する理論的研究","袖山 慶太郎, 隅田 真人, 館山 佳尚","袖山 慶太郎, 隅田 真人, 館山 佳尚","日本物理学会2011年秋季大会","日本物理学会2011年秋季大会","2011-09-21","","jpn","oral_presentation","","","","","","","色素増感太陽電池のエネルギー変換効率を系統的に向上させていくためには、分子レベルにおける界面の構造を理解することが必要不可欠である。本発表では二酸化チタンアナターゼ(101)表面におけるブラックダイの吸着構造および励起状態に関して、第一原理計算による検討を行った。特に色素のカルボキシル基に存在するプロトンが、表面に吸着後どの位置にあるのが最も安定であるかは色素の設計上非常に重要な情報であるため、それぞれの構造について計算を行い安定性を比較した。その結果、プロトンが色素側に残ったままの構造の方が、色素から離れて表面に吸着した構造よりも安定であることを明らかにした。さらにそれらの構造における励起状態計算を行った結果、プロトンが色素側に存在する構造におけるUV-visスペクトルが実験値とよい相関を示すことを確認した。" "光触媒系二酸化チタン/水界面の吸着水と水素結合に関する第一原理分子動力学解析","光触媒系二酸化チタン/水界面の吸着水と水素結合に関する第一原理分子動力学解析","隅田 真人, Chunping Hu, 館山 佳尚","隅田 真人, Chunping Hu, 館山 佳尚","分子科学討論会","分子科学討論会","2011-09-20","","jpn","oral_presentation","","","","","","","アナターゼ型二酸化チタンの(101)面と(001)面上のバルクの水の様子を,第一原理分子動力学法を用いて探索した.その結果,水分子は(101)面では分子吸着され,(001)面においては解離吸着されている事が確認された.吸着された水分子はバルクの水の水素結合ネットワークに参加しており,表面に数層の水分子を置いた従来の計算結果とは異なる吸着構造を取っている.さらに,より詳細な解析の結果によって,水バルク中と比べて弱い水素結合は(001)面上のみに現れる事が分かった.この結果は1H-NMRの結果とも一致する事を報告する." "溶液および固液界面の電子状態:第一原理分子動力学アプローチ","溶液および固液界面の電子状態:第一原理分子動力学アプローチ","館山 佳尚","館山 佳尚","第23回液体の化学夏の学校2011 ","第23回液体の化学夏の学校2011 ","2011-09-13","","jpn","oral_presentation","","","","","","","溶液反応・固液界面反応を理解するには、構造揺らぎ・電子状態揺らぎの両者を考慮する必要があります。溶質・溶媒・固体の電子状態を考慮しながら液体ダイナミクスを取り扱える第一原理分子動力学(MD)計算は、その最有力ソリューションです。計算機能力の向上と共に扱えるサイズ・サンプリング数・計算精度とも向上し、様々な系を扱えるようになってきました。" "固液界面の大規模第一原理計算","固液界面の大規模第一原理計算","隅田 真人, 袖山 慶太郎, 館山 佳尚","隅田 真人, 袖山 慶太郎, 館山 佳尚","第2回「学際計算科学による新たな知の発見・統合・創出」シンポジウ","第2回「学際計算科学による新たな知の発見・統合・創出」シンポジウ","2011-09-12","","jpn","oral_presentation","","","","","","","アナターゼ型二酸化チタンの(101)面と(001)面上のバルクの水の様子を,第一原理分子動力学法を用いて探索した .その結果,水分子は(101)面では分子吸着され,(001)面においては解離吸着されている事が確認された.吸着さ れた水分子はバルクの水の水素結合ネットワークに参加しており,表面に数層の水分子を置いた従来の計算結果と は異なる吸着構造を取っている.さらに,より詳細な解析の結果によって,水バルク中と比べて弱い水素結合は(0 01)面上のみに現れる事が分かった.この結果は1H-NMRの結果とも一致する事を報告する." "Adsorption and excitation of black-dye on TiO2 anatase(101) surface for dye-sensitized solar cells","色素増感太陽電池開発に向けた二酸化チタンアナターゼ(101)表面上におけるブラックダイの吸着構造および励起状態に関する理論的研究","袖山 慶太郎, 隅田 真人, 館山 佳尚","袖山 慶太郎, 隅田 真人, 館山 佳尚","ISTCP-VII (Congress of the International Society for Theoretical","ISTCP-VII (Congress of the International Society for Theoretical","2011-09-02","","jpn","oral_presentation","","","","","","","高効率な色素増感太陽電池開発のため、本発表では二酸化チタンアナターゼ(101)表面に吸着するブラックダイの吸着構造および励起状態に関して理論的検討を行った。第一原理計算により考え得る4種類の吸着構造を求めた結果、色素のカルボキシル基と表面のチタン原子との結合が1本である構造の方が2本の場合よりも安定であることを明らかにした。これは、結合が1本の場合には色素が自由に回転できるために色素と表面の間に水素結合ができること、さらに配位子が構造的に歪む影響による。また色素にプロトンが残ったままの構造の方が表面にプロトンが移動した場合よりも安定であることも明らかにした。その構造における励起状態計算を行ったところ、UV-visスペクトルが実験値とよい相関を示した。プロトンの存在する位置により太陽電池の効率は大きく変化すると言われており、本構造は新しい設計メカニズムに対する新しいコンセプトを提案している。" "Interface Water on TiO2 Anatase (101) and (001) Surfaces: First-Principles Study with TiO2 Slabs Dipped in Bulk Water","Interface Water on TiO2 Anatase (101) and (001) Surfaces: First-Principles Study with TiO2 Slabs Dipped in Bulk Water","隅田 真人, Chunping Hu, 館山 佳尚","隅田 真人, Chunping Hu, 館山 佳尚","ISTCP-VII","ISTCP-VII","2011-09-02","","jpn","oral_presentation","","","","","","","We investigated the TiO2 anatase (101) and (001) interfaces dipped in bulk water on the atomic scale by first-principles density-functional molecular dynamics (MD) simulations. We verified that the water adsorption models proposed in the previous studies with less than a couple of water layers on the vacuum surfaces still hold. On the contrary, novel adsorption structures of interfacial water molecules are also found. " "Computational study on photo- and thermo-reactions between tetra-tert-butyl-substituted cyclobutadiene and tetrahedrane","Computational study on photo- and thermo-reactions between tetra-tert-butyl-substituted cyclobutadiene and tetrahedrane","隅田 真人, 齋藤 一弥, 館山 佳尚","隅田 真人, 齋藤 一弥, 館山 佳尚","ISTCP-VII","ISTCP-VII","2011-09-02","","jpn","oral_presentation","","","","","","","We have investigated the photo-chemical reaction from tetra-tert-butylcyclobutadiene (TB-CBD) to tetra-tert-butyltetrahedrane (TB-THD) and its reverse thermo-chemical reaction processes in the ground state [1] by using CASSCF and MRMP2 computational methods." "Organic-Metallic Hybrid Polymers: Effect of Substituent on DNA Binding Properties","Organic-Metallic Hybrid Polymers: Effect of Substituent on DNA Binding Properties","李 菁華, フテラ ズデニェク, 館山 佳尚, 村上 達也, 樋口 昌芳","李 菁華, フテラ ズデニェク, 館山 佳尚, 村上 達也, 樋口 昌芳","第60回高分子学会年次大会","第60回高分子学会年次大会","2011-05-25","","jpn","oral_presentation","","","","","","","Herein, we synthesized novel organic-metallic hybrid polymers. The interaction between polymer and ct-DNA was investigated by UV, CV, CD, luminescence, AFM, and electronic structure calculation. All results are supportive of electrostatic mode of binding." "Ab initio investigation of ZrO2-CeO2 interface properties","Ab initio investigation of ZrO2-CeO2 interface properties","フロンジ マルコ, Alessandro DeVita, 館山 佳尚, トラベルサ エンリコ","フロンジ マルコ, Alessandro DeVita, 館山 佳尚, トラベルサ エンリコ","The 219th ECS meeting","The 219th ECS meeting","2011-05-01","","jpn","oral_presentation","","","","","","","In the present work we use a computational Density Functional Theory approach to investigate the structural and electronic properties of the (100) and (111) ZrO2-CeO2 interface. Optimisation of the lattice geometry for the separate ZrO2 and CeO2 bulks as well as the interface is carried out and the structural morphology is analysed. The energy formation of the oxygen vacancies are analysed at different values of lattice parameter, in order to verify its dependency on the strain." "Conjugation of Organic-Metallic Hybrid Polymers and Calf-Thymus DNA","Conjugation of Organic-Metallic Hybrid Polymers and Calf-Thymus DNA","李 菁華, フテラ ズデニェク, 館山 佳尚, MURAKAMI Tatsuya, 樋口 昌芳","李 菁華, フテラ ズデニェク, 館山 佳尚, MURAKAMI Tatsuya, 樋口 昌芳","日本化学会第91春季年会","日本化学会第91春季年会","2011-03-26","","jpn","oral_presentation","","","","","","","Organic-metallic hybrid polymers were synthesized by self-assembly. The conjugation of polymers and calf-thymus DNA were investigated by UV titration, CD, CV, luminescence, AFM, and electronic structure calculation. The cell cytotoxicity was also studied." "First-principles study on Ru(4,4","TiO2アナターセ(101)表面に吸着したRu(4,4","袖山 慶太郎, 隅田 真人, 館山 佳尚","袖山 慶太郎, 隅田 真人, 館山 佳尚","APS march meeting 2011","APS march meeting 2011","2011-03-21","","jpn","oral_presentation","","","","","","","For the improvement of the power conversion of DSSC, we need to understand the adsorbed structures at atomistic level in detail. In this study, we investigated the adsorbed structures of Ru(4,4" "Conductive Polymer Chain Wiring to a Functional Molecule via Chemical Soldering","ケミカルソルダリングを用いた機能分子への導電性高分子鎖配線","大川 祐司, マンダル スワパン クマー, 胡 春平, 館山 佳尚, GOEDECKER Stefan, 塚本 茂, 長谷川 剛, ジムジェウスキー ジェイムス, 青野 正和","大川 祐司, マンダル スワパン クマー, 胡 春平, 館山 佳尚, GOEDECKER Stefan, 塚本 茂, 長谷川 剛, ジムジェウスキー ジェイムス, 青野 正和","MANA International Symposium 2011","MANA International Symposium 2011","2011-03-02","","jpn","oral_presentation","","","","","","","For making electric connections to individual functional molecules, a method to wire single molecules with conductive organic polymers is required. We have developed a method using a probe tip of scanning tunneling microscope (STM) to control the chain polymerization of diacetylene compounds on a self-ordered layers, thereby creating single chains of conductive polydiacetylene (PDA). Here we show our recent experimental and theoretical results how conductive polymers can be connected to a functional molecule via covalent bonds. The propagating ends of chain polymerization have reactive chemical species and therefore react with the adsorbed molecule and form chemical bonds spontaneously. We call this method “chemical soldering”." "First-principles calculation study on redox reactivity of diamond(111)/water interface","First-principles calculation study on redox reactivity of diamond(111)/water interface","館山 佳尚","館山 佳尚","MANA International Symposium 2011","MANA International Symposium 2011","2011-03-02","","jpn","oral_presentation","","","","","","","Redox (electron transfer) reactions on solid/solution interfaces play crucial roles in diverse topics in energy & environmental issues such as fuel cell, solar cell, catalysis, corrosion. However, the microscopic mechanisms of those reactions are still matters of debate, and the elucidation at the atomic scale is highly desired for the theoretical reaction design in the future. For the theoretical simulation, we have developed a first-principles (FP) molecular dynamics (MD) technique to calculate electronic chemical potential of electrode, flat band potential (FBP) and potential of zero charge (PZC). This technique is based on the Marcus theory of electron transfer as well as the fundamentals of density functional theory (DFT), and using the physicochemical concept that the electrode bias" "Ab initio investigation of ZrO2-CeO2 interface properties","Ab initio investigation of ZrO2-CeO2 interface properties","フロンジ マルコ, Alessandro Vita, 館山 佳尚, トラベルサ エンリコ","フロンジ マルコ, Alessandro Vita, 館山 佳尚, トラベルサ エンリコ","15th International Workshop on Computational Physics and Materia","15th International Workshop on Computational Physics and Materia","2011-01-13","","jpn","oral_presentation","","","","","","","In the present work we present a Density Functional Theory approach to investigate the structural and electronic properties of the low index ZrO2-CeO2 interface. Optimizations of the crystal geometry for the separate ZrO2 and CeO2 bulks as well as the interfaces are carried out and the structural morphology is analyzed." "QM/MM Study of Piano-Stool Ru(II) Complexes Interacting with DNA","QM/MM Study of Piano-Stool Ru(II) Complexes Interacting with DNA","フテラ ズデニェク, 館山 佳尚, Jaroslav V. Burda","フテラ ズデニェク, 館山 佳尚, Jaroslav V. Burda","物性研・CMSI・次世代ナノ情報 合同研究会 「計算物質科学の課題と展","物性研・CMSI・次世代ナノ情報 合同研究会 「計算物質科学の課題と展","2011-01-05","","jpn","oral_presentation","","","","","","","Purpose of this project is to look at interaction of [(eta6-ben)RuII(en)Cl]+ complex with DNA, especially on structural changes of double-helix, and compare it with behaviour of cisplatin. It is well known that anti-cancer activity of cisplatin is caused by forming intra-strand cross-link between two adjacent guanines and we want to check possibility of this mechanism also in case of Ru(II) complex." "ZrO2-CeO2 interface properties : a first-principle investigation","ZrO2-CeO2 interface properties : a first-principle investigation","フロンジ マルコ, 館山 佳尚, トラベルサ エンリコ, Alessandro Vita","フロンジ マルコ, 館山 佳尚, トラベルサ エンリコ, Alessandro Vita","物性研・CMSI・次世代ナノ情報 合同研究会 「計算物質科学の課題と展","物性研・CMSI・次世代ナノ情報 合同研究会 「計算物質科学の課題と展","2011-01-05","","jpn","oral_presentation","","","","","","","In the present work we use a computational Density Functional Theory approach to investigate the structural and electronic properties of the low index ZrO2-CeO2 interface. Optimization of the lattice geometry for the separate ZrO2 and CeO2 bulks as well as the interface is carried out and the structural morphology is analyzed." "First-Principles MD Study on Proton Diffusion in Anhydrous Perfluorosulfonic Acid – 1,2,3-Triazole Blend Membrane for PEFCs","First-Principles MD Study on Proton Diffusion in Anhydrous Perfluorosulfonic Acid – 1,2,3-Triazole Blend Membrane for PEFCs","田中 喜典, 館山 佳尚, 井上 純一, 全 文錫, 金 済徳","田中 喜典, 館山 佳尚, 井上 純一, 全 文錫, 金 済徳","MRS-J","MRS-J","2010-12-20","","jpn","oral_presentation","","","","","","","Here, we discuss proton diffusion in anhydrous perfluorosulfonic acid (Nafion)–1,2,3-triazole blend membranes by first-principles molecular dynamics (MD) to understand additional insight into the membrane structure and function. The first-principles MD simulations are carried out in the framework of DFT (density functional theory) method implemented in Car-Parrinello molecular dynamics (CPMD) with generalized gradient corrected exchange-correlation functional. Calculated diffusion constant of 1,2,3-triazole in perfluorosulfonic acid is a couple of order larger in magnitude than that of water. Although the result shows low mobility, that implies a potential ability of anhydrous alternative way of proton diffusion in electrolytes." "Interface Water on TiO2 Anatase (101) and (001) Surfaces: First-Principles Study with TiO2 Slabs Dipped in Bulk Water","バルク水を用いた第一原理固液界面シミュレーションによるTiO2 アナターゼ(101)・(001) /水 界面の解析","館山 佳尚, 隅田 真人, 胡 春平","館山 佳尚, 隅田 真人, 胡 春平","20th MRS-J Academic Symposium","20th MRS-J Academic Symposium","2010-12-20","","jpn","oral_presentation","","","","","","","We investigated the TiO2 anatase (101) and (001) interfaces dipped in bulk water on the atomic scale by first-principles density-functional molecular dynamics (MD) simulations. We verified that the water adsorption models proposed in the previous studies with less than a couple of water layers on the vacuum surfaces still hold. On the contrary, novel adsorption structures of interfacial water molecules are also found. Our results indicate that water molecules around the interface between the TiO2 and bulk water can be described by a two-layer model" "Computational photo and thermo reactions between tetra-tert-butyl-cyclobutadiene and tetrahedrane","Computational photo and thermo reactions between tetra-tert-butyl-cyclobutadiene and tetrahedrane","隅田 真人, 館山 佳尚, 齋藤 一弥","隅田 真人, 館山 佳尚, 齋藤 一弥","Pacifichem 2010","Pacifichem 2010","2010-12-15","","jpn","oral_presentation","","","","","","","We have investigated the photo- and thermo-chemical reaction processes between tetra-tert-butylcyclobutadiene (TB-CBD) and tetra-tert-butyltetrahedrane (TB-THD) by using CASSCF and MRMP2 computational methods. Our results indicate that the photochemical reaction from TB-CBD to TB-THD occurs via the dipole forbidden HOMO-LUMO double electron excited state (21A1 state). After the excitation to the 21A1 state, most TB-CBD shows only photophysical property without any reactions because the final point of the minimum-energy-path (MEP) calculation at the MRMP2//CASSCF level is the S1/S0 conical intersection (CI), which has ionic like structure, leading to turning back to TB-CBD in the S0 state. " "Conjugation of organic-metallic hybrid polymers and DNA for application to DD","Conjugation of organic-metallic hybrid polymers and DNA for application to DD","李 菁華, フテラ ズデニェク, 李 紅芳, 館山 佳尚, 樋口 昌芳","李 菁華, フテラ ズデニェク, 李 紅芳, 館山 佳尚, 樋口 昌芳","2010 International Chemical Congress of Pacific Basin Societies","2010 International Chemical Congress of Pacific Basin Societies","2010-12-15","","jpn","oral_presentation","","","","","","","The interaction of metal complexes with nucleic acids has aroused much interest in the development of novel DNA structure probes or new reagents for biotechnology and medicine. Metallo-supramolecular coordination polyelectrolytes (MEPEs) were obtained by self-assembly complexation of the ditopic bis-terpyridines with metal ions [Ru(II), Fe(II)]. The DNA binding studies between MEPEs and ct-DNA were investigated through UV-vis titration experiment, circular dichroism, cyclic voltammetry, atomic force microscope and electronic structure calculation. The results are supportive of electrostatic inte" "Wiring a single functional molecule by using conductive linear polymers","導電性ポリマー鎖による単一機能性分子の配線","大川 祐司, マンダル スワパン クマー, 胡 春平, 館山 佳尚, GOEDECKER Stefan, 塚本 茂, 長谷川 剛, 青野 正和","大川 祐司, マンダル スワパン クマー, 胡 春平, 館山 佳尚, GOEDECKER Stefan, 塚本 茂, 長谷川 剛, 青野 正和","ElecMol10","ElecMol10","2010-12-06","","jpn","oral_presentation","","","","","","","We propose and demonstrate a novel method for connecting conductive polymers to a single functional molecule. Chain polymerization was initiated by applying a pulsed bias voltage to the row of diacetylene molecules to which a phthalocyanine pentamer is adsorbed, and the resulting polydiacetylene chain was connected to the phthalocyanine molecule. Similarly, we succeeded in connecting two polydiacetylene chains to the same phthalocyanine molecule. The method developed in the present study will represent a key step in realizing future single-molecule devices." "TiO2/H2O界面における吸着構造、水素結合および酸化還元能","TiO2/H2O界面における吸着構造、水素結合および酸化還元能","館山 佳尚","館山 佳尚","第8回水素量子アトミクス研究会","第8回水素量子アトミクス研究会","2010-10-27","","jpn","oral_presentation","","","","","","","環境・エネルギー問題に関連する化学反応のほとんどが酸化還元反応(電子移動反応)といっても過言ではないでしょう。さらに触媒、電池系ではその反応の多くが固液界面で起こります。この「固液界面での酸化還元反応」の電子・原子レベルからの理解はまだ完全にはほど遠い状態です。このような状況を理論計算側から解明すべく、我々は様々な酸化還元反応に対する第一原理分子動力学(MD)計算手法の開発・確立を行い、溶液系・固液界面系を用いて実証してきました。本講演では最近の題材を含めて、その一端を紹介したいと思います。" "TiO2/H2O界面における吸着構造、水素結合および酸化還元能","TiO2/H2O界面における吸着構造、水素結合および酸化還元能","館山 佳尚","館山 佳尚","グリーンイノベーションのための表面・界面化学/分子研研究会","グリーンイノベーションのための表面・界面化学/分子研研究会","2010-10-05","","jpn","oral_presentation","","","","","","","We investigated structural and electronic properties of the TiO2 anatase (101) and (001) surfaces dipped in water by first-principles density-functional molecular dynamics simulations, aiming at understanding the microscopic mechanism of photocatalytic reactions on the TiO2 interfaces. In contrast to the previous studies with only a few layers of H2O molecules on vacuum TiO2 surfaces, we used supercells involving bulk water on the TiO2 slabs and found some characteristics in the presence of bulk water. Our results indicate a two-layer model for interfacial water molecules on the TiO2 surfaces." "Wiring a single phthalocyanine molecule using polydiacetylene","フタロシアニン単分子へのポリジアセチレンによる分子ナノ配線","大川 祐司, マンダル スワパン クマー, 胡 春平, 館山 佳尚, GOEDECKER Stefan, 塚本 茂, 長谷川 剛, 青野 正和","大川 祐司, マンダル スワパン クマー, 胡 春平, 館山 佳尚, GOEDECKER Stefan, 塚本 茂, 長谷川 剛, 青野 正和","第4回分子科学討論会2010大阪","第4回分子科学討論会2010大阪","2010-09-14","","jpn","oral_presentation","","","","","","","機能性有機単分子に、単一の導電性高分子鎖を接続する方法を確立することは、単分子の電気特性の解明や、将来の単分子デバイスの開発に向けて極めて重要である。我々が提案する新しい方法では、我々がこれまで開発してきた、有機分子の連鎖重合反応を走査トンネル顕微鏡(STM)の探針により制御する方法を用い、連鎖重合反応の活性末端の自発的化学反応を利用する。本講演では、機能分子としてフタロシアニンを用いてこの方法による分子ナノ配線を実証し、さらに第一原理理論計算に基づく議論を行う。" "FMO法に基づく三体項を導入した電子状態計算手法の開発","FMO法に基づく三体項を導入した電子状態計算手法の開発","小堀 知輝, 館山 佳尚, 袖山 慶太郎, 常行 真司","小堀 知輝, 館山 佳尚, 袖山 慶太郎, 常行 真司","分子科学討論会2010","分子科学討論会2010","2010-09-14","","jpn","oral_presentation","","","","","","","近年北浦和夫氏により開発されたフラグメント分子軌道(FMO)法は、第一原理に基づく生体分子のためのシミュレーション手法として注目を集めている。本研究では、FMO法に基づいて、系全体の電子状態を直感的にわかりやすい形で、効率的に求める新しい電子状態計算手法(FMO-LCMO法)を紹介する。本研究では、従来のFMO法で計算される各フラグメントおよびそのダイマー(およびトライマー)の一電子ハミルトニアンを組み合わせることで、系全体のハミルトニアンを構成する。組み合わせる際は、各部分系のハミルトニアンを表現する基底関数を原子軌道からフラグメント分子軌道に変換する。言い換えれば、系の電子状態は各フラグメントの分子軌道の線形結合(Linear Combination of Molecular Orbitals)で表現されることになる。" "QM/MM Study of Piano-Stool Ru(II) Complexes Interacting with DNA","QM/MM Study of Piano-Stool Ru(II) Complexes Interacting with DNA","フテラ ズデニェク, 館山 佳尚, Jaroslav V. Burda","フテラ ズデニェク, 館山 佳尚, Jaroslav V. Burda","4th Annual Meeting of Japan Society for Molecular Science (2010)","4th Annual Meeting of Japan Society for Molecular Science (2010)","2010-09-14","","jpn","oral_presentation","","","","","","","Piano-stool Ru(II) complexes is a group of biologically active compounds with promising anti-cancer activity. Their interaction with DNA is known from experimental measurements but the exact reaction mechanism is not well described yet. QM/MM computational methodology is applied to study hydration and consequent binding of [(benzene)Ru(II)(en)Cl]+ complex to DNA. Structure as well as electronic properties will be presented." "円錐型交差から見たシクロブタジエンとテトラへドラン間の基底状態ポテンシャルエネルギー曲面","円錐型交差から見たシクロブタジエンとテトラへドラン間の基底状態ポテンシャルエネルギー曲面","隅田 真人, 齋藤 一弥, 館山 佳尚","隅田 真人, 齋藤 一弥, 館山 佳尚","第4回分子科学討論会2010大阪","第4回分子科学討論会2010大阪","2010-09-14","","jpn","oral_presentation","","","","","","","CASSCF計算を用いて,S1/S0 円錐型交差から基底状態PES (S0 PES)を計算し,無置換テトラへドラン分子から,シクロブタジエンへの対称性禁制反応を解析した.無置換テトラへドラン分子の単離の可能性について議論するとともに,円錐型交差からS0 PESの解析を行う事が有用である事を示す." "Water structure and redox reactivity of TiO2 anatase / water interfaces: Firstprinciples MD study with TiO2 slabs soaked in bulk water","Water structure and redox reactivity of TiO2 anatase / water interfaces: Firstprinciples MD study with TiO2 slabs soaked in bulk water","館山 佳尚, 隅田 真人, 胡 春平","館山 佳尚, 隅田 真人, 胡 春平","Psi-K conference 2010","Psi-K conference 2010","2010-09-12","","jpn","oral_presentation","","","","","","","We investigated the interface properties of the TiO2 anatase (101) and (001) surfaces " "Water structure of TiO2 anatase/waer interfaces:First-principles MD study with TiO2 slabs soaked in bulk water ","Water structure of TiO2 anatase/waer interfaces:First-principles MD study with TiO2 slabs soaked in bulk water ","館山 佳尚, 隅田 真人, 胡 春平","館山 佳尚, 隅田 真人, 胡 春平","CECAM workshop "Titania for all seasons"","CECAM workshop "Titania for all seasons"","2010-09-06","","jpn","oral_presentation","","","","","","","We investigated the interface properties of the TiO2 anatase (101) and (001) surfaces " "Density-functional molecular dynamics study on interfacial water ","Density-functional molecular dynamics study on interfacial water ","館山 佳尚, 隅田 真人, 胡 春平","館山 佳尚, 隅田 真人, 胡 春平","240th ACS National meeting","240th ACS National meeting","2010-08-22","","jpn","oral_presentation","","","","","","","Redox reactions play crucial roles in diverse topics in energy & environmental issues such as battery, fuel cell and catalysis. For theoretical simulations of such reactions, several ab initio calculation methods have been recently proposed, most of which focus on the potential variation near electrodes. We have taken a different strategy of using free energy to calculate the redox properties. In fact, fundamental quantities of redox reactions are characterized by free energies, which are mainly governed by structural fluctuations along with electron transfer (ET). Combining the idea of Marcus theory of ET, thermodynamic integration scheme, with density-functional (DF) molecular dynamics (MD), we have established ab initio calculation methods for redox free energies" "First-principles MD study on redox reaction ability of semiconductor/water interfaces","First-principles MD study on redox reaction ability of semiconductor/water interfaces","館山 佳尚","館山 佳尚","CECAM workshop ","CECAM workshop ","2010-07-12","","jpn","oral_presentation","","","","","","","we focus on electron transfer reaction across the interface. To obtain quantities associated with this " "Interfacial water on TiO2 anatase/bulk water interfaces: first-principles molecular dynamics via TiO2 slabs dipped in bulk water ","Interfacial water on TiO2 anatase/bulk water interfaces: first-principles molecular dynamics via TiO2 slabs dipped in bulk water ","館山 佳尚, 隅田 真人, 胡 春平","館山 佳尚, 隅田 真人, 胡 春平","STAC4","STAC4","2010-06-21","","jpn","oral_presentation","","","","","","","We carried out density-functional Car-Parrinello molecular dynamics simulations of the TiO2 surfaces dipped in bulk water using slab model with periodic boundary condition at room temperature (See Figure). Our simulations show that all fivefold Ti atoms (Ti5c) on the (101) surface undergo molecular adsorption of water, and dissociative adsorption predominantly occurs on the (001) surface, which basically confirms the recent suggestion based on the calculations using multi-layer water models in Prof. Selloni group. However, we obtained more detailed information of interfacial water structure" "Ab Initio Free Energy Calculation Methods for Redox Reactions","Ab Initio Free Energy Calculation Methods for Redox Reactions","館山 佳尚","館山 佳尚","International Conference on Core Research and Engineering Scienc","International Conference on Core Research and Engineering Scienc","2010-05-31","","jpn","oral_presentation","","","","","","","Redox reactions play crucial roles in diverse topics in energy & environmental issues such as battery, fuel cell and catalysis. For theoretical simulations of such reactions, several ab initio calculation methods have been recently proposed, most of which focus on the potential variation near electrodes. We have taken a different strategy of using free energy to calculate the redox properties. Combining the idea of Marcus theory of ET, thermodynamic integration scheme, with density-functional (DF) molecular dynamics (MD), we have established ab initio calculation methods for redox free energies" "第一原理計算による固液界面での酸化還元反応解析","第一原理計算による固液界面での酸化還元反応解析","館山 佳尚","館山 佳尚","日本化学会第90春季年会","日本化学会第90春季年会","2010-03-26","","jpn","oral_presentation","","","","","","","「固液界面での酸化還元反応」の電子・原子レベルからの理解はまだ完全にはほど遠い状態です。このような状況を理論計算側から解明すべく、我々は様々な酸化還元反応に対する第一原理分子動力学(MD)計算手法の開発・確立を行い、溶液系・固液界面系を用いて実証してきました。本講演では最近の題材を含めて、その一端を紹介したいと思います。" "Interfacial water on TiO2 anatase (101) and (001) surfaces by first-principles molecular dynamics with TiO2 slabs dipped in bulk water","Interfacial water on TiO2 anatase (101) and (001) surfaces by first-principles molecular dynamics with TiO2 slabs dipped in bulk water","館山 佳尚","館山 佳尚","Workshop on "Materials Nanoarchitectonics for Sustainable D","Workshop on "Materials Nanoarchitectonics for Sustainable D","2010-03-22","","jpn","oral_presentation","","","","","","","We carried out density-functional Car-Parrinello molecular dynamics simulations of the TiO2 surfaces dipped in bulk water using slab model with periodic boundary condition at room temperature. Our simulations show that all fivefold Ti atoms (Ti5c) on the (101) surface undergo molecular adsorption of water, and dissociative adsorption predominantly occurs on the (001) surface, which basically confirms the recent suggestion based on the calculations using multi-layer water models in Prof. Selloni group. However, we obtained more detailed information of interfacial water structure." "First-principles study of chain polymerization on surfaces: Large-scale calculations using BigDFT","BigDFTを用いた大規模第一原理計算による表面連鎖重合反応メカニズムの考察","胡 春平, 館山 佳尚, Stefan Goedecker, 大川 祐司, 青野 正和","胡 春平, 館山 佳尚, Stefan Goedecker, 大川 祐司, 青野 正和","日本物理学会第65回年次大会","日本物理学会第65回年次大会","2010-03-20","","jpn","oral_presentation","","","","","","","ナノスケールデバイス(細線、スイッチなど)の効率的作成方法として表面上の有機分子膜の連鎖重合反応の利用に期待がよせられている。我々はグラファイト表面上に自己組織化された有機分子(ジアセチレン化合物のモノマー)膜の上にさらに機能性分子(フタロシアニン:Pc)を置いた時に、連鎖重合反応の進行が抑制されるというSTM観測に対して、大規模第一原理計算による構造安定性の比較を通して、その連鎖反応の進行メカニズムに対する理論的検討を行った。" "TiO2 anatase/水界面の水分子吸着に関する 第一原理分子動力学シミュレーション ","TiO2 anatase/水界面の水分子吸着に関する 第一原理分子動力学シミュレーション ","館山 佳尚, 隅田 真人, 胡 春平","館山 佳尚, 隅田 真人, 胡 春平","日本物理学会2010年春季大会","日本物理学会2010年春季大会","2010-03-19","","jpn","oral_presentation","","","","","","","代表的な光触媒系であるTiO2 アナターゼはすでに多くの応用例があるものの、水溶液との界面で起こっている原子スケールの反応メカニズムー光誘起有害分子分解(酸化)や超親水化などーは未だに良く分かっていない。そのような問題を明らかにするため、我々は第一原理MDを用いた自由エネルギーをベースとする酸化還元反応解析に取り組んでいる。本講演ではその第一段階であるTiO2 アナターゼ(101)及び(001)/水界面の平衡状態解析の結果について報告する1" "Interfacial water on TiO2 anatase (101) and (001) surfaces by first-principles molecular dynamics with TiO2 slabs dipped in bulk water","Interfacial water on TiO2 anatase (101) and (001) surfaces by first-principles molecular dynamics with TiO2 slabs dipped in bulk water","館山 佳尚","館山 佳尚","MANA International Symposium 2010","MANA International Symposium 2010","2010-03-03","","jpn","oral_presentation","","","","","","","We carried out density-functional Car-Parrinello molecular dynamics simulations of the TiO2 surfaces dipped in bulk water using slab model with periodic boundary condition at room temperature. Our simulations show that all fivefold Ti atoms (Ti5c) on the (101) surface undergo molecular adsorption of water, and dissociative adsorption predominantly occurs on the (001) surface, which basically confirms the recent suggestion based on the calculations using multi-layer water models in Prof. Selloni group. However, we obtained more detailed information of interfacial water structure." "Nonadiabatic couplings from time-dependent density functional theory: Recent progress","時間依存密度汎関数理論による非断熱結合の計算:最近の進展","胡 春平, 杉野修, 館山 佳尚","胡 春平, 杉野修, 館山 佳尚","ナノ統合シミュレーションソフトウェアの研究開発第4回公開シンポ","ナノ統合シミュレーションソフトウェアの研究開発第4回公開シンポ","2010-03-03","","jpn","oral_presentation","","","","","","","我々は、時間依存密度汎関数理論による非断熱結合の厳密な計算式を導出した。平面波・擬ポテンシャル近似で実証した結果、様々の系で計算精度が良好であることを確認した。一方、擬ポテンシャル近似の問題点も明らかになった。そこで、我々はさらに全電子・原子基底計算手法を開発し、非断熱結合の計算の妥当性を系統的に調べることを行った。" "First-principles molecular dynamics study on water adsorption and interfacial water on TiO2 anatase/bulk water interfaces","First-principles molecular dynamics study on water adsorption and interfacial water on TiO2 anatase/bulk water interfaces","隅田 真人, 胡 春平, 館山 佳尚","隅田 真人, 胡 春平, 館山 佳尚","NIMS International Workshop on Photocatalysis and Environmental ","NIMS International Workshop on Photocatalysis and Environmental ","2010-02-22","","jpn","oral_presentation","","","","","","","We carried out large-scale first-principles density-functional molecular dynamics simulations of TiO2 surfaces dipped in bulk water for the first time, using slab model with periodic boundary condition. BLYP generalized gradient corrected exchange-correlation functional, plane wave basis set up to the energy cutoff of 70 Ry with Troullier-Martin type norm-conserving pseudopotentials were used. Concerning molecular dynamics, we used Nosé-Hoover thermostat with the temperature of 300 K for NVT and time step of 5 a.u. (ca. 0.12 fsec)." "Ultrafast Lattice Dynamics of Graphite under Intense Photoexcitation","強い光励起下でのグラファイトの超高速格子ダイナミクス","石岡 邦江, 籾田 浩義, 館山 佳尚, 北島 正弘, 大野 隆央","石岡 邦江, 籾田 浩義, 館山 佳尚, 北島 正弘, 大野 隆央","International Symposium on the Physics of Excitation-assisted N","International Symposium on the Physics of Excitation-assisted N","2009-11-20","","jpn","oral_presentation","","","","","","","Irradiationn of femtosecond laser pulses below the ablation threshold generates coherent phonons as well as photocarriers in graphite. In the present study, we investigate the interlayer (E2g1) lattice dynamics of graphite under intense laser excitation beyond the harmonic limit but below the ablation threshold. Transient reflectivity shows an amplitude beating above a threshold laser pulse energy. We carry out first-principles calculations based on the density functional theory with the local density approximation to examine possible reason for the observed result. " "Connection of polydiacetylene nanowires to a single functional molecule via covalent bonds","単一機能性分子へのポリジアセチレンナノワイヤーの共有結合による接続","大川 祐司, マンダル スワパン クマー, 長谷川 剛, 塚本 茂, 胡 春平, 館山 佳尚, ヒル ジョナサン, 有賀 克彦, 青野 正和","大川 祐司, マンダル スワパン クマー, 長谷川 剛, 塚本 茂, 胡 春平, 館山 佳尚, ヒル ジョナサン, 有賀 克彦, 青野 正和","MNC 2009","MNC 2009","2009-11-16","","jpn","oral_presentation","","","","","","","We show our recent experimental and theoretical results which demonstrate the connection of polydiacetylene nanowires to a single phthalcyanine molecule via covalent bonds." "第一原理MDサンプリングによる固液界面酸化還元反応の解析","第一原理MDサンプリングによる固液界面酸化還元反応の解析","館山 佳尚","館山 佳尚","次世代ナノ・連続研究会:燃料電池(No.3)","次世代ナノ・連続研究会:燃料電池(No.3)","2009-11-16","","jpn","oral_presentation","","","","","","","触媒、電池系ではその反応の多くが固液界面で起こります。この「固液界面での酸化還元反応」の電子・原子レベルからの理解はまだ完全にはほど遠い状態です。このような状況を理論計算側から解明すべく、我々は様々な酸化還元反応に対する第一原理分子動力学(MD)計算手法の開発・確立を行い、溶液系・固液界面系を用いて実証してきました。本講演では最近の題材を含めて、その一端を紹介したいと思います。" "Nonadiabatic couplings from time-dependent density functional theory: Recent progress","Nonadiabatic couplings from time-dependent density functional theory: Recent progress","胡 春平, 杉野修, 館山 佳尚","胡 春平, 杉野修, 館山 佳尚","The 12th Asian Workshop on First-Principles Electronic Structure","The 12th Asian Workshop on First-Principles Electronic Structure","2009-10-26","","jpn","oral_presentation","","","","","","","Nowadays it is recognized that conical intersections of potential energy surfaces (PES) are ubiquitous in chemical systems. The existence of these crossing points renders the Born-Oppenheimer approximation break down: not only PES but also nonadiabatic couplings (NAC) are needed for nonadiabatic simulations. Recently we presented a rigorous formulation of NAC from time-dependent density functional theory and carried out extensive calculations around various types of intersections. Challenges of the pseudopotential approximation were revealed for the computation of NAC. The comparison study in the all-electron framework has further verified this point, and shown that it is necessary to make assessment on exchange-correlation effects near intersection points." "Preparation and Optical Properties of Fullerene/Ferrocene Hybrid Hexagonal Nanosheets","フラーレン/フェロセンハイブリッドナノシートの合成と光物性","若原 孝次, 宮澤 薫一, マラパン サティス, 胡 春平, 館山 佳尚, 根本 善弘, 佐々木 敏雄, 伊藤攻","若原 孝次, 宮澤 薫一, マラパン サティス, 胡 春平, 館山 佳尚, 根本 善弘, 佐々木 敏雄, 伊藤攻","NMS-V","NMS-V","2009-10-18","","jpn","oral_presentation","","","","","","","We herein report a simple method for the preparation of C60/Fc hybrid nanowhiskers and hexagonal nanosheets by a liquid-liquid interfacial precipitation (LLIP) method. The highly crystallized C60/ferrocene hexagonal nanosheets had the formulation C60(ferrocene)2. A strong charge-transfer (CT) band between ferrocene and C60 was observed at 782 nm, indicating the presence of donor-acceptor interaction in the nanosheets. Upon heating the nanosheets to 150 C, the CT band disappeared due to the sublimation of ferrocene from the C60/ferrocene hybrid, and C60 nanosheets with an fcc crystal structure and the same shape and size as the C60/ferrocene nanosheets were obtained. " "Excited-State Dynamics of Spin-Polarized Systems by Time-Dependent Density Functional Theory (TDDFT)","TDDFTによるspin-polarized系の励起状態ダイナミクス計算","胡 春平, 宮本良之, 館山 佳尚","胡 春平, 宮本良之, 館山 佳尚","日本物理学会2009年秋季大会","日本物理学会2009年秋季大会","2009-09-25","","jpn","oral_presentation","","","","","","","時間依存密度汎関数法(TDDFT)は電子励起ダイナミクスを第一原理的にかつ効率的に記述する手法として注目を浴びている。しかし、これまでのTDDFTによる電子励起ダイナミクスの研究はsinglet励起を対象としspin-unpolarized系で取り扱うというものがほとんどであった。一方実在系においては光学活性を持つ開殻分子(ラジカル)や電荷を加えられた閉殻分子などのspin-polarized系におけるtripletやdoublet励起も光化学反応の重要な過程となっている。そのメカニズム解明や光誘起スピン制御の模索するためには、スピンのあらわな取り扱いが必要不可欠となっている。そのため、我々は実時間発展TDDFTプログラムFPSEIDのspin-polarized系に対する拡張を行った。さらに、典型的な分子に応用してFranck-Condon励起状態からのダイナミクスを計算した。" "Ab-initio double-face slab model for redox reactions on solid/solution interfaces","両面スラブモデルによる固液界面酸化還元反応の第一原理解析 ","館山 佳尚, 渡辺剛志, 栄長泰明","館山 佳尚, 渡辺剛志, 栄長泰明","日本物理学会2009年秋季大会","日本物理学会2009年秋季大会","2009-09-25","","jpn","oral_presentation","","","","","","","電池や触媒において最も重要な過程は電極/溶液界面における電子移動反応・酸化還元反応である。物質合成を目的としたバイアス印加反応に対して、エネルギー抽出・抑制に焦点をあてたゼロバイアスでの現象も数多く存在する。本研究はこのゼロバイアス下において、固液界面の酸化還元反応を特徴づける物理量を第一原理分子動力学計算から求めることを試みた。" "Z-ペンタ-2,4-ジエニミニウムのhydrogen-out-of-plane motion先導による光異性化反応経路","Z-ペンタ-2,4-ジエニミニウムのhydrogen-out-of-plane motion先導による光異性化反応経路","隅田 真人, 齋藤一弥, 館山 佳尚","隅田 真人, 齋藤一弥, 館山 佳尚","第3回分子科学討論会2009","第3回分子科学討論会2009","2009-09-21","","jpn","oral_presentation","","","","","","","レチナールプロトン化シッフ塩基のモデル分子,ペンタ-2,4-ジエニミニウム (PDI)のZからEへの光異性化では,第一励起状態(S1)に光励起の後,中央の炭素骨格(C-C-C-Cの二面角)が大きく変化することによって,S1から基底状態(S0)へ遷移する事が理論的に主張されている.本研究では,MRMP2//CASSC計算によりポテンシャルエネルギー曲面を探索し,hydrogen-out-of-plane motion(HOOP: H-C-C-Hの二面角)が炭素骨格の変化よりも先行することによって,励起状態上での炭素骨格の大きな変化が無くとも,S1からS0への遷移が可能であることを報告する." "半導体電極/水溶液界面における酸化還元電位及び 電子移動反応の第一原理解析","半導体電極/水溶液界面における酸化還元電位及び 電子移動反応の第一原理解析","館山 佳尚, 渡辺剛志, 栄長泰明","館山 佳尚, 渡辺剛志, 栄長泰明","第3回分子科学討論会2009名古屋","第3回分子科学討論会2009名古屋","2009-09-21","","jpn","oral_presentation","","","","","","","触媒、燃料電池、太陽電池などの効率向上を目指した研究は数多く行われているものの、その最もキーとなる電極/電解質溶液界面における酸化還元・電子移動反応の詳細については、まだ不明な点が数多く残されている。真空表面に比べ固液界面における電子・原子スケールでの観測が難しいことがその大きな要因で、その困難を乗り越えるべく元来電子・原子を取り扱ってきた第一原理計算からの理論的アプローチが待望されている。本研究ではその一つの方向性を実証することを目的とする。" "Molecular nanowiring using single conductive polymers","単一導電性高分子による分子ナノ配線","大川 祐司, マンダル スワパン クマー, 長谷川 剛, 塚本 茂, 胡 春平, 館山 佳尚, ヒル ジョナサン, 有賀 克彦, 青野 正和","大川 祐司, マンダル スワパン クマー, 長谷川 剛, 塚本 茂, 胡 春平, 館山 佳尚, ヒル ジョナサン, 有賀 克彦, 青野 正和","第58回高分子討論会","第58回高分子討論会","2009-09-16","","jpn","oral_presentation","","","","","","","走査トンネル顕微鏡探針を用いたジアセチレン化合物の連鎖重合反応のナノスケール制御と、基板上の単一ポリジアセチレンの構造、およびこれを利用した機能性有機分子への単一分子配線について議論する。" "Photoexcited Electron-Ion Dynamics within Time-Dependent Density Functional Theory","Photoexcited Electron-Ion Dynamics within Time-Dependent Density Functional Theory","胡 春平, 宮本良之, 館山 佳尚","胡 春平, 宮本良之, 館山 佳尚","ChinaNANO 2009","ChinaNANO 2009","2009-09-01","","jpn","oral_presentation","","","","","","","First principles calculation based on density functional theory (DFT) has become a main technique for the modeling and simulation of nanostructures at the atomistic level. For the investigation of excited-state dynamics in nano-systems, time-dependent DFT (TDDFT) with the real-time propagation (RTP) technique is most promising. However, previous work on this aspect is still rather limited, and lacks the control of spin. Also, nonadiabatic effects near the crossing points of potential energy surfaces are yet to be taken into account. Bearing this in mind, we have recently extended the TDDFT-RTP program package FPSEID to treat spin-polarized systems and make validations for TDDFT-RTP applications to nonadiabatic processes involved in photoexcited electron-ion dynamics." "Preparation and Optical Properties of Fullerene/Ferrocene Hybrid Hexagonal Nanosheets","フラーレン/フェロセンハイブリッドナノシートの合成と光物性","若原 孝次, マラパン サティス, 宮澤 薫一, 胡 春平, 館山 佳尚, 根本 善弘, 佐々木 敏雄, 伊藤攻","若原 孝次, マラパン サティス, 宮澤 薫一, 胡 春平, 館山 佳尚, 根本 善弘, 佐々木 敏雄, 伊藤攻","第37回フラーレン・ナノチューブ総合シンポジウム","第37回フラーレン・ナノチューブ総合シンポジウム","2009-09-01","","jpn","oral_presentation","","","","","","","We herein report a simple method for the preparation of C60/Fc hybrid nanowhiskers and hexagonal nanosheets by a liquid-liquid interfacial precipitation (LLIP) method. The highly crystallized C60/ferrocene hexagonal nanosheets had the formulation C60(ferrocene)2. A strong charge-transfer (CT) band between ferrocene and C60 was observed at 782 nm, indicating the presence of donor-acceptor interaction in the nanosheets. Upon heating the nanosheets to 150 C, the CT band disappeared due to the sublimation of ferrocene from the C60/ferrocene hybrid, and C60 nanosheets with an fcc crystal structure and the same shape and size as the C60/ferrocene nanosheets were obtained. " "Nonadiabatic couplings from time-dependent density functional theory: Pseudopotential and all-electron schemes","Nonadiabatic couplings from time-dependent density functional theory: Pseudopotential and all-electron schemes","胡 春平, 杉野修, 館山 佳尚","胡 春平, 杉野修, 館山 佳尚","GRC: Time-Dependent Density-Functional Theory","GRC: Time-Dependent Density-Functional Theory","2009-07-05","","jpn","oral_presentation","","","","","","","Nonadiabatic couplings (NACs) are of central quantity in nonadiabatic processes. Recently we presented a rigorous formula to calculate NACs between the ground and excited states of molecules, using time-dependent density functional theory. Implemented in the plane wave pseudopotential framework, it has been confirmed that our formalism can efficiently calculate NACs near various types of intersections of potential energy surfaces. On the other hand, it was found that the pseudopotential approximation might give inaccurate results for some NACs components on nonhydrogen atoms. Therefore, we have carried out all-electron calculation using atomic orbital basis sets. The results show that the sum rule is well satisfied and good accuracy can be achieved." "Ab initio MD study on redox reactions on semiconductor/water interface ","Ab initio MD study on redox reactions on semiconductor/water interface ","館山 佳尚","館山 佳尚","The 8th Japan-France Workshop on Nanomaterials","The 8th Japan-France Workshop on Nanomaterials","2009-06-15","","jpn","oral_presentation","","","","","","","In order to establish ab initio calculation techniques for such quantities, we have carried out extensive ab initio molecular dynamics (MD) for semiconductor/water interfaces and compared the results with the experimental one available. In the calculations, we adopt double face slab model for easy and straightforward control of water density. With the MD trajectories, we have calculated average features of water molecule distribution as well as electronic states, and found their dependence on the interface structure of the electrode. " "時間依存密度汎関数法による非断熱結合係数の計算手法:全電子・原子基底での実証研究","時間依存密度汎関数法による非断熱結合係数の計算手法:全電子・原子基底での実証研究","胡 春平, 杉野修, 館山 佳尚","胡 春平, 杉野修, 館山 佳尚","第12回理論化学討論会","第12回理論化学討論会","2009-05-28","","jpn","oral_presentation","","","","","","","断熱ポテンシャル面と非断熱結合係数(NAC)は、非断熱量子シミュレーションの2本柱である。空間サンプリング数は膨大であることから、従来の波動関数に基づく量子化学的手法よりも効率の良い計算手法が求められている。我々は時間依存密度汎関数法でNACの厳密な計算式を導出した。平面波擬ポテンシャル枠組みで精度を検証したところ、擬ポテンシャル近似を改良する必要があることがわかった。そのためにはNACの全電子計算手法を開発し、原子基底に基づき実証研究を行った。その場合、原子基底の原子座標依存性があることから、いわゆるPulay補正の項を考えなければならない。また、原子基底が通常直交していないので、原子基底で求められたNACの諸要素を正規直交基底にあらわに変換する必要がある。我々のNAC計算結果には量子化学手法CASSCFよりかなり良い精度でsum ruleが成り立つことがわかった。" "Computational study on influence of vacancy-related defects accumulation on hydrogen embrittlement of steels","水素脆性に影響を及ぼす空孔等の点欠陥蓄積に関する計算科学的研究","大野 隆央, 浅利 裕介, 籾田 浩義, 中村 美道, 館山 佳尚","大野 隆央, 浅利 裕介, 籾田 浩義, 中村 美道, 館山 佳尚","鉄鋼材料の革新的高強度・高機能化基盤研究開発第1回シンポジウム","鉄鋼材料の革新的高強度・高機能化基盤研究開発第1回シンポジウム","2009-04-14","","jpn","oral_presentation","","","","","","","高強度材料の信頼性を高めるためには、水素脆化による低温遅れ破壊防止の設計指針構築が重要な課題であり、実材料中の様々な欠陥組織因子にトラップされた水素を定量的に分離し評価することが強く求められる。本研究では、粒界水素偏析量の定量的評価に資することを目的に、粒界と競合する代表的な水素トラップ因子である空孔・空孔集合体における水素存在状態、及び偏析量を大規模第一原理計算により定量的に解析した。その結果、空孔への水素トラップエネルギーや水素と空孔の相互作用などに関する定量的評価を獲得し、空孔集合体の形成メカニズムと、それに対する水素の効果を明らかにした。また、結晶粒界の引張強度に対する水素、空孔、及び水素空孔複合体の偏析による効果を調べ、原子レベルの粒界水素脆化メカニズムを考察した。" "All-Electron Calculation of Nonadiabatic Couplings from Time-Dependent Density Functional Theory (TDDFT)","TDDFTによる非断熱結合係数の全電子計算手法","胡 春平, 杉野修, 館山 佳尚","胡 春平, 杉野修, 館山 佳尚","日本物理学会第64回年次大会","日本物理学会第64回年次大会","2009-03-27","","jpn","oral_presentation","","","","","","","非断熱結合係数(NAC)は非断熱過程において中心的な役割を果たす。しかし、NACの定義式が多体波動関数に基づいているため、長い間密度汎関数法(DFT)での取り扱いが困難だと考えられてきた。これに対して我々はTime-Dependent DFT線形応答理論に基づく計算が可能であろうと考え、計算式を導出し分子の基底状態と励起状態の間のNACを系統的に調べてきた。平面波擬ポテンシャル枠組みで実装したところ、CI法等の波動関数に基づく量子化学的方法に比べて効率的に計算を行うことができ、水素原子や一価元素では計算精度も良好であることが確認できた。他の元素では必ずしも計算精度が保証されず、それが少なくとも擬ポテンシャルに起因していることも明らかになった。そこで、今回全電子計算手法を開発し、TD-DFTによるNACの計算の妥当性を系統的に調べることとした。" "Ab initio MD strudy on properties of diamond/water interface","第一原理MDによるダイヤモンド電極/水溶液界面の構造および電子状態","館山 佳尚, 渡辺剛志, 栄長泰明","館山 佳尚, 渡辺剛志, 栄長泰明","日本物理学会2009年春季大会","日本物理学会2009年春季大会","2009-03-27","","jpn","oral_presentation","","","","","","","我々はこのダイヤモンド電極/水溶液界面で起こる酸化還元反応メカニズムの電子・原子スケールからの理解を目標に、第一原理MDを用いた理論的かつ定量的反応解析にも取り組んだ。その第一段階として固液界面スラブモデルを用いて、ボロンドープ量・界面構造・電解質種類の異なる様々な条件における室温下での(準)安定界面構造およびその電子状態を計算した。" "Development of order-N DFT methods and the applications on nano materials","第一原理オーダーN手法の開発とナノ物質への応用 ","大野 隆央, 宮崎 剛, 木野 日織, 西野 正理, 奈良 純, 館山 佳尚, 大塚 教雄","大野 隆央, 宮崎 剛, 木野 日織, 西野 正理, 奈良 純, 館山 佳尚, 大塚 教雄","特定領域「次世代量子デザイン」第4回成果報告会 ","特定領域「次世代量子デザイン」第4回成果報告会 ","2009-03-23","","jpn","oral_presentation","","","","","","","科研費特定領域「次世代量子シミュレータ・量子デザイン手法の開発」における研究課題「第一原理オーダーN手法の開発とナノ物質への応用」の平成20年度の研究成果を報告する。" "Ab initio free energy approach to redox reaction in solution and on solid/solution interface","Ab initio free energy approach to redox reaction in solution and on solid/solution interface","館山 佳尚","館山 佳尚","2009 WPI-AIMR annual workshop","2009 WPI-AIMR annual workshop","2009-03-02","","jpn","oral_presentation","","","","","","","We have applied novel methods to redox reactions of transition metal complexes in aqueous solution, and successfully demonstrated their accuracy on standard redox potential and reorganization energy. Recently we have been examining redox reactions with an explicit semiconductor/water interface as well, which is still underway. Irrespective of the approximation of electric double layer, reasonable results are obtained concerning the structural stability, while the treatment of carrier control seems to need further development." "Ab initio MD study on redox reactions in electrolyte solution of DSSC","Ab initio MD study on redox reactions in electrolyte solution of DSSC","館山 佳尚","館山 佳尚","MANA International symposium 2009","MANA International symposium 2009","2009-02-25","","jpn","oral_presentation","","","","","","","We have applied these methods to redox reactions associated with triiodide (I3-) and iodide (I-) ions in typical electrolyte solutions of dye-sensitised solar cell (DSSC). In spite of many applications as electrolyte, the atomistic mechanisms of these iodide redox reactions have not been fully understood due to the complex nature involving multiple electron transfers and bond changes. " "Ab initio MD study on redox reactions in electrolyte solution","電解質溶液中電子移動反応の第一原理シミュレーション","館山 佳尚","館山 佳尚","特定領域「量子デザイン」A02班ミニワークショップ","特定領域「量子デザイン」A02班ミニワークショップ","2009-01-16","","jpn","oral_presentation","","","","","","","I applied novel methods we have developed to redox reactions associated with iodide and triiodide ions in solution. My calculations of redox free energies and reaction pathways of several elementary processes of this redox couple indicate that reduction and bond breaking are competitive in the solvated triiodide systems and there seems a significant solvent dependence." "Free energies of redox (electron transfer) reactions of iodides in solution","Free energies of redox (electron transfer) reactions of iodides in solution","館山 佳尚","館山 佳尚","14th International Workshop on Computational Physics and Materia","14th International Workshop on Computational Physics and Materia","2009-01-08","","jpn","oral_presentation","","","","","","","I applied novel methods we have developed to redox reactions associated with iodide and triiodide ions in solution. My calculations of redox free energies and reaction pathways of several elementary processes of this redox couple indicate that reduction and bond breaking are competitive in the solvated triiodide systems and there seems a significant solvent dependence." "Overestimation of excitation energy in DFT and TDDFT calculation","Overestimation of excitation energy in DFT and TDDFT calculation","館山 佳尚, 胡 春平, 大塚 教雄","館山 佳尚, 胡 春平, 大塚 教雄","次世代ナノ情報機能・材料グループ成果報告会","次世代ナノ情報機能・材料グループ成果報告会","2008-12-10","","jpn","oral_presentation","","","","","","","we have done a re-assessment of the conventional DFT-KS and TDDFT-LR formalisms for excitation energy, by using a transition metal oxide molecule as a test case." "固液界面酸化還元反応の理論的反応設計技術の構築","固液界面酸化還元反応の理論的反応設計技術の構築","館山 佳尚","館山 佳尚","さきがけ・CREST合同領域会議","さきがけ・CREST合同領域会議","2008-09-27","","jpn","oral_presentation","","","","","","","理論面では固液界面系における標準酸化還元電位や電子移動の活性化自由エネルギーを定量的に記述できる新しい第一原理自由エネルギー計算手法の確立を行うことを主目標に、関連する固液界面の安定配置探索や先端計算手法を用いた光吸収・励起ダイナミクス解析にも取り組んでおります。応用面では、PCやDSSCに密接につながる酸化物・半導体電極/水溶液・電解質溶液系に焦点をあて、未だ不明な点が多い界面近傍の原子スケールでの構造・酸化還元反応過程の基礎的知見増大に取り組んでいます。本講演では最近取り組んだ(1)DSSC電解質溶液中の酸化還元反応メカニズム解析と(2)ダイヤモンド電極化学センサー界面の反応メカニズム解析について報告します。" "Overestimation problem on excitation energy in the DFT/TDDFT framework","DFT/TDDFTにおける励起エネルギー「過大」評価問題","館山 佳尚, 大塚 教雄, Sprik Michiel","館山 佳尚, 大塚 教雄, Sprik Michiel","第2回分子科学討論会","第2回分子科学討論会","2008-09-24","","jpn","oral_presentation","","","","","","","溶液効果を量子的に考慮した分子の光吸収スペクトルに対する理論計算の精度評価という動機のもと代表的な酸化剤である過酸 化マンガンイオン(MnO-4 ) 水溶液の光吸収スペクトルについて水分子を露に取り扱ったDFTおよびTDDFT 計算を行なった。その結果TDDFT-BLYP レベルですでに励起エネルギーを過大評価し、非局所Hartree-Fock(HF) 交換項を入れるとそれが悪化するという結果を得た。この問題に焦点をあて議論する。" "Theoretical formulation and accuracy evaluation of nonadiabatic couplings from time-dependent density functional theory","時間依存密度汎関数法による非断熱結合係数の厳密な計算式および精度の検証","胡 春平, 平井宏俊, 杉野修, 館山 佳尚","胡 春平, 平井宏俊, 杉野修, 館山 佳尚","第2回分子科学討論会","第2回分子科学討論会","2008-09-24","","jpn","oral_presentation","","","","","","","断熱ポテンシャル面が交差する場合には非断熱結合係数(NAC)が無限大になるのでBorn-Oppenheimer近似は破綻する。このため交差付近では NAC項をあらわに考える必要がある。その計算には多体波動関数が必要になるためこれまでCIなどの量子化学の手法に頼ってきた。しかし、大規模な系を計算するためには、他の高効率な計算を用いる必要がある。この点に注目し、我々は時間依存密度汎関数法で分子の基底状態と励起状態の間のNACを計算する手法を開発した。講演ではまずKohn-Sham系に基づくNACの厳密な計算式を示し、次に拡張線形応答理論を用いた精度の改善について述べる。テスト計算の結果、単純な分子ではCI並みの精度が達成されることが分かった。" "First-principles calculation of hydrogen-defect interaction in iron","鉄中の水素‐欠陥相互作用に関する第一原理計算","籾田 浩義, 浅利 裕介, 館山 佳尚, 大野 隆央","籾田 浩義, 浅利 裕介, 館山 佳尚, 大野 隆央","日本金属学会2008年度秋季大会","日本金属学会2008年度秋季大会","2008-09-23","","jpn","oral_presentation","","","","","","","水素による鋼の脆性破壊は重要な問題であるが、特に電子・原子スケールにおける微視的な水素脆化メカニズムは完全な理解には至っていない。最近、鉄における原子空孔の重要性が理論および実験の両方から指摘されている。それらの結果によると、水素と空孔は互いに強く相互作用し、それらの複合体が安定化することが示されている。本研究では、第一原理計算を用いて、この複合体が相互に又は他の欠陥とどのように相互作用するかを調べた。計算の結果、バルク中においては複数の水素空孔複合体の間に強い相互作用が見出された。すなわち、それらが空間的に離れて存在するよりも、より大きなクラスターを形成する方がエネルギー的に安定である。空孔および水素空孔複合体が相互に又は他の欠陥とどのように相互作用するかを示し、より現実的な系における空孔の挙動を考察する。" "Ab-initio MD simulation study on trihalides in solution","三ハロゲン化物イオン溶液に関する第一原理分子動力学シミュレーション","館山 佳尚","館山 佳尚","日本物理学会2008年秋季大会","日本物理学会2008年秋季大会","2008-09-20","","jpn","oral_presentation","","","","","","","本研究では第一原理MDシミュレーションを用いて水溶液中のX3-イオン(X=Cl,Br,I)の平衡構造・電子状態をまず求めた。さらに結合・解離反応中の水和構造の効果を検討すべく、X-, X2イオン水溶液との比較も行なった。さらにヨウ素に焦点をあて電子移動反応、化学結合変化に対する反応自由エネルギーを我々が最近開発した第一原理拘束MDエネルギーギャップ法[1]を用いて解析した。" "Ab-initio MD Methods for Free Energies of Chemical Reactions Coupled to Electron Transfer","Ab-initio MD Methods for Free Energies of Chemical Reactions Coupled to Electron Transfer","館山 佳尚, Blumberger Jochen, Sprik Michiel","館山 佳尚, Blumberger Jochen, Sprik Michiel","WATOC2008","WATOC2008","2008-09-14","","jpn","oral_presentation","","","","","","","“Redox reactions”, play crucial roles in diverse topics such as battery, fuel cell, catalysis, corrosion, photosynthesis, Fundamental aspects of redox reactions are characterised by free energies in which electronic states and structural ensemble play crucial roles. However, few methods can take both into account. We have developed ab-initio methods for free energy calculation of redox reactions, namely electron transfer and change of chemical bonds:Density-Functional Molecular Dynamics Energy gap (DF-MD-EG) method, DF Constrained MD EG (DF-CMD-EG) method. We have demonstrated that both DF-MD-EG and DF-CMD-EG methods enable us to do quantitative calculation of redox free energies energies & estimation of probable reaction pathways even for complicated redox reactions. " "Ab initio study on hydrogen-defect interaction in alpha-Fe and its role in hydrogen embrittlement","Ab initio study on hydrogen-defect interaction in alpha-Fe and its role in hydrogen embrittlement","籾田 浩義, 浅利 裕介, 館山 佳尚, 大野 隆央","籾田 浩義, 浅利 裕介, 館山 佳尚, 大野 隆央","2008 International Hydrogen Conference","2008 International Hydrogen Conference","2008-09-07","","jpn","oral_presentation","","","","","","","Microscopic mechanism of the hydrogen embrittlement of steel has not been fully understood especially at the atomic and electronic scale. Recently, importance of vacancies was pointed out. Aim of this study is to clarify the behavior of the hydrogen atoms, the iron vacancies, and their complexes in the alpha-Fe, and to show their effects onto the mechanical properties by means of ab initio calculations. In the bulk, the clusters consisting of the hydrogen-vacancy complexes are proven to be energetically more stable than those being separately. The results also indicate that the hydrogen, the vacancies, and the complexes are energetically more stable on the grain boundaries than in the bulk region. We discuss their effects onto the mechanical properties." "Ab initio molecular dynamics study on iodide redox (electron transfer) reactions in solution","Ab initio molecular dynamics study on iodide redox (electron transfer) reactions in solution","館山 佳尚","館山 佳尚","The 1st International Conference of the Grand Challenge to Next-","The 1st International Conference of the Grand Challenge to Next-","2008-06-03","","jpn","oral_presentation","","","","","","","We have applied these methods to redox reactions associated with iodide (I-) and triiodide (I-3 ) ions in solution. These iodides are often used as a redox couple in several applications. Also they are related to famous iodine titration. However the atomistic mechanisms of the redox reactions haven’t been fully understood. There are some issues such as the symmetry breaking of solvated I-3 , I-I bond breaking coupled to ET, and so on. Our calculations of redox potentials of the elementary processes imply that the reduction of triiodide is a trigger of the series of processes in aqueous solution." "Overestimation of excitation energy in DFT and TDDFT calculations","Overestimation of excitation energy in DFT and TDDFT calculations","館山 佳尚, 大塚 教雄, Leonardo Bernasconi, Michiel Sprik","館山 佳尚, 大塚 教雄, Leonardo Bernasconi, Michiel Sprik","International Conference on Quantum Simulators and Design 2008","International Conference on Quantum Simulators and Design 2008","2008-05-31","","jpn","oral_presentation","","","","","","","We have done a re-assessment of the conventional DFT-KS and TDDFT-LR formalisms for excitation energy, by using a transition metal oxide molecule as a test case. We found that (1) the KS orbital energy differences well reproduce the experimental excitation energies and (2) the LR-TDDFT overestimates the excitation energies significantly. In order to understand this extraordinary behaviour, we have investigated the contribution of solvent which exists in the experimental observation as well as the pseudopotential and exchangecorrelation effects in the calculations. It seems that electron correlation plays a certain role for that." "Development of order-N DFT methods and the applications on nano materials","第一原理オーダーN手法の開発とナノ物質への応用","大野 隆央, 宮崎 剛, 木野 日織, 西野 正理, 奈良 純, 館山 佳尚, 大塚 教雄","大野 隆央, 宮崎 剛, 木野 日織, 西野 正理, 奈良 純, 館山 佳尚, 大塚 教雄","特定領域研究「次世代量子シミュレータ・量子デザイン手法の開発と応","特定領域研究「次世代量子シミュレータ・量子デザイン手法の開発と応","2008-03-18","","jpn","oral_presentation","","","","","",""," 超大規模解析が可能な第一原理オーダーN手法の開発を中心として、安定構造・反応経路探索法、伝導特性解析法、励起状態解析法等のナノ物質の解析に有効な手法の確立を目指した研究を遂行しており、超大規模シミュレーションにより、ナノ物質の新奇な物性・機能の量子論的な解析・予測、構造と機能の相関関係の解明、新奇な機能の設計とその実現のための構造の提案等、ナノ構造の機能探索・設計に関する量子論的研究を進めたので、その結果を発表する。" "Novel First-Principles Molecular Dynamics Method for Free Energy Analysis of Redox Reaction","Novel First-Principles Molecular Dynamics Method for Free Energy Analysis of Redox Reaction","館山 佳尚","館山 佳尚","MANA International Symposium 2008","MANA International Symposium 2008","2008-03-10","","jpn","oral_presentation","","","","","","","For quantitative analysis of redox reactions, we have recently developed novel first-principles molecular dynamics methods based on density functional theory, statistical mechanics and Marcus theory of electron transfer." "第一原理計算から見た鉄中の水素ー空孔・欠陥相互作用","第一原理計算から見た鉄中の水素ー空孔・欠陥相互作用","館山 佳尚","館山 佳尚","「水素脆化研究の基盤構築」フォーラム","「水素脆化研究の基盤構築」フォーラム","2008-03-07","","jpn","oral_presentation","","","","","","","鉄鋼材料の水素脆性破壊の微視的メカニズムを最終目標に行われた鉄ー水素ー空孔・欠陥系に関する一連の第一原理計算の紹介およびその結果から導きだされる有望メカニズムの紹介。" "固液界面酸化還元反応の理論的反応設計技術の構築1","固液界面酸化還元反応の理論的反応設計技術の構築1","館山 佳尚","館山 佳尚","JSTさきがけ研究領域「界面の構造と制御」第3回領域会議","JSTさきがけ研究領域「界面の構造と制御」第3回領域会議","2008-01-05","","jpn","oral_presentation","","","","","","","私の研究課題「固液界面酸化還元反応の理論的反応設計技術の構築」の研究構想説明。" "Computational electrochemistry: new first-principles method for electrochemical reactions","Computational electrochemistry:電気化学反応に対する新規第一原理アプローチ","館山 佳尚","館山 佳尚","東大物性研短期研究会「物性化学のフロンティア2007」","東大物性研短期研究会「物性化学のフロンティア2007」","2007-11-20","","jpn","oral_presentation","","","","","",""," 表面化学分野では第一原理計算による解析が非常に浸透しており、既に標準的なツールとして認知されていると言っても過言ではない。しかしそれは真空表面という限定的な環境に対するもので、実用的なマテリアル中の環境である固固界面、固液界面、溶液系に対しては現状の第一原理計算ではまだまだ不十分な点が多い。近年このようなモチベーションからより一般的な物理化学反応に対する様々な新規第一原理計算アプローチが国内外から提案されてきた。我々もその一つとして,電気化学の基本反応である酸化還元反応の定量的解析を可能にする第一原理自由エネルギー計算手法-Density Functional Constrained Molecular Dynamics Energy Gap method(DF-CMD-EG method)-の開発と実証を行った。" "Overestimation of excitation energy in the DFT/TDDFT calculations","DFT/TDDFT計算による励起エネルギー過大評価問題","館山 佳尚, 大塚 教雄, L. Bernasconi, M. Sprik","館山 佳尚, 大塚 教雄, L. Bernasconi, M. Sprik","日本物理学会第62回年次大会","日本物理学会第62回年次大会","2007-09-21","","jpn","oral_presentation","","","","","","","我々は線形応答TDDFTと平面波基底の第一原理MD を組み合わせることにより、これまで困難であった溶液系の光吸収計算に取り組んだ。その精度実証として紫色を示す過酸化マンガンイオン水溶液について計算を行った所、TDDFT計算のみならず通常のDFT計算においても励起エネルギーを’過大’評価することがわかった。講演では交換・相関項依存性の吟味や量子化学計算との比較を行いながらその原因について議論する。" "酸化還元反応に対するab initio自由エネルギー計算手法の開発","酸化還元反応に対するab initio自由エネルギー計算手法の開発","館山 佳尚, Jochen Blumberger, 大野 隆央, Michiel Sprik","館山 佳尚, Jochen Blumberger, 大野 隆央, Michiel Sprik","第一回分子科学討論会","第一回分子科学討論会","2007-09-17","","jpn","oral_presentation","","","","","","","電子移動を伴う化学結合の開裂/形成反応、いわゆる酸化還元反応はエネルギー・環境問題に関連する多くの問題のキープロセスである。しかしそれらの自由エネルギーを計算できるab initio計算手 法はこれまでなかった。本研究では熱力学積分法を出発点としMarcus energy gap法およびBlue-moon統計などを用いることにより電子移動と化学結合変化を同時に取り扱える新しいab initio自由エネルギー計算手法を開発した。さらに水溶液中の遷移金属酸化物イオンによる「水分解」反応に適用し、精度実証をするとともにプロトン移動機構などの反応メカニズムを明らかにした。それらにつ いて報告する。" "Water addition along with reduction of aqueous ruthenium complexes by ab initio free energy calculation method for bond breaking/formation coupled to electron transfer","Water addition along with reduction of aqueous ruthenium complexes by ab initio free energy calculation method for bond breaking/formation coupled to electron transfer","館山 佳尚, Jochen Blumberger, 大野 隆央, Michiel Sprik","館山 佳尚, Jochen Blumberger, 大野 隆央, Michiel Sprik","American Chemical Society 234th national meeting & exposition","American Chemical Society 234th national meeting & exposition","2007-08-19","","jpn","oral_presentation","","","","","","","We have developed a DFT-based ab initio free energy calculation method for change of chemical bonds coupled to electron transfer by combining constrained molecular dynamics with the energy gap method for redox free energy. The formulation is derived based on the thermodynamic integration scheme, thus quite general. We have also suggested a special way to choose an efficient scalar constraint for reactions with multiple relevant reaction coordinates. " "Density-functional constrained molecular dynamics energy gap (DF-CMD-EG) method for free energy calculation of chemical reaction coupled to electron transfer","Density-functional constrained molecular dynamics energy gap (DF-CMD-EG) method for free energy calculation of chemical reaction coupled to electron transfer","館山 佳尚","館山 佳尚","FADFT2007","FADFT2007","2007-08-01","","jpn","oral_presentation","","","","","","","We have applied this DF-CMD-EG method to a water cleavage reaction coupled to electron transfer on a transition metal oxide ion in aqueous solution and demonstrated that it can well reproduce experimental reaction free energy." "Development of ab-initio free energy calculation method for bond breaking/formation coupled to electron transfer","電子移動に伴う結合開裂・形成反応向けの第一原理自由エネルギー計算手法の開発","館山 佳尚","館山 佳尚","「次世代ナノ情報機能・材料」成果報告会","「次世代ナノ情報機能・材料」成果報告会","2007-07-13","","jpn","oral_presentation","","","","","","","我々は酸化還元反応の記述に向けた新しい第一原理自由エネルギー計算手法の開発・実証に取り組んできた。その中で最近、電子移動を伴う化学結合切断/形成反応(例えば A + B + e- --> AB-)の反応・活性化自由エネルギー計算を可能にする「第一原理拘束MDエネルギーギャップ法」を開発した。" "Development of order-N DFT methods and the applications on nano materials","第一原理オーダーN手法の開発とナノ物質への応用","大野 隆央, 宮崎 剛, 木野 日織, 西野 正理, 奈良 純, 館山 佳尚","大野 隆央, 宮崎 剛, 木野 日織, 西野 正理, 奈良 純, 館山 佳尚","科研費特定領域研究「次世代量子シミュレータ〜」平成19年度顔合わせ会議","科研費特定領域研究「次世代量子シミュレータ〜」平成19年度顔合わせ会議","2007-06-08","","jpn","oral_presentation","","","","","","","超大規模シミュレーションにより、ナノ物質の新奇な物性・機能の量子論的な解析・予測、構造と機能の相関関係の解明、新奇な機能の設計とその実現のための構造の提案等、ナノ構造の機能探索・設計に関する量子論的アプローチを目指す研究の概要を紹介する。(1) 超大規模シミュレーション手法の開発、(2) ナノバイオ・ナノ触媒系への適用、(3) ナノ物質の構造と機能の解明、(4) ナノ物質の新機能の設計、の流れで遂行する研究計画を説明する。" "第一原理オーダーN手法の開発とナノ物質への応用","第一原理オーダーN手法の開発とナノ物質への応用","大野 隆央, 宮崎 剛, 木野 日織, 西野 正理, 奈良 純, 館山 佳尚, 大塚 教雄, 尾崎泰助","大野 隆央, 宮崎 剛, 木野 日織, 西野 正理, 奈良 純, 館山 佳尚, 大塚 教雄, 尾崎泰助","科研費特定領域研究 「次世代量子シミュレータ・量子デザイン手法の","科研費特定領域研究 「次世代量子シミュレータ・量子デザイン手法の","2007-03-23","","jpn","oral_presentation","","","","","","","科研費特定領域研究「次世代量子シミュレータ・量子デザイン手法の開発と応用」のA02班、大野班の平成18年度の研究成果を紹介する。" "励起状態グラファイトのE2gフォノンに関する理論的研究","励起状態グラファイトのE2gフォノンに関する理論的研究","籾田 浩義, 館山 佳尚, 大野 隆央","籾田 浩義, 館山 佳尚, 大野 隆央","日本物理学会2007年春季大会","日本物理学会2007年春季大会","2007-03-18","","jpn","oral_presentation","","","","","","","最近、ポンプ・プローブ法によってグラファイトのコヒーレントフォノンが観測され、高密度の電子励起に対してE2g振動数領域に2つの振動数ピークが存在することが報告されている。この2つのピークの起源を明らかにするために第一原理計算に基づいた理論的研究を行った。励起キャリアの緩和過程を考慮して計算したエネルギー曲面をもちいて、励起状態グラファイトのE2gフォノンに関する議論を行う。" "New ab initio method for free energy calculation of the reaction with bond change coupled to electron transfer","電子移動を伴う結合開裂・形成反応に対する第一原理自由エネルギー計算手法の開発","館山 佳尚, 大野 隆央, Jochen Blumberger, Michiel Sprik","館山 佳尚, 大野 隆央, Jochen Blumberger, Michiel Sprik","日本物理学会2007年春季大会","日本物理学会2007年春季大会","2007-03-18","","jpn","oral_presentation","","","","","","","酸化還元反応は燃料電池、光触媒、光合成をはじめとする多くの興味深い現象の 素過程である。その多くが電子移動を伴う結合開裂・形成反応とみなすことできる。 我々はこれまで電子移動反応のみに対する第一原理自由エネルギー計算手法を 開発してきた。本研究ではそれを拡張し電子移動を伴う結合開裂・形成反応に 適用可能なより一般的な自由エネルギー計算手法の開発を世界で初めて行った。" "実時間発展TDDFTによる分子系光励起状態の電子ー核ダイナミクス","実時間発展TDDFTによる分子系光励起状態の電子ー核ダイナミクス","館山 佳尚, 小山 紀久, 大野 隆央, 宮本良之","館山 佳尚, 小山 紀久, 大野 隆央, 宮本良之","次世代ナノ統合シミュレーションソフトウェアの研究開発第1回公開シ","次世代ナノ統合シミュレーションソフトウェアの研究開発第1回公開シ","2007-03-05","","jpn","oral_presentation","","","","","","","視物質内タンパクの光化学反応、光駆動スイッチなど光励起ダイナミクスが絡んだ現象は大変注目を集めている。近年のレーザー技術の進展により光励起後の過渡状態スペクトルが観測可能になり、光励起ダイナミクスの理解が大きく前進した。しかし観測スペクトル(振動数)から電子・原子核ダイナミクスを翻訳するには、まだ様々な不確定要素が絡み困難な場合も多い。そこで我々は量子力学の基本方程式から出発したTDDFT実時間発展形式を用いて電子・原子核の動きを直接かつ定量的に追跡することに取り組んだ。本講演ではその理論・計算手法について述べた後、その実証計算として行った光励起開環反応の結果について紹介する。" "Free energy computation of reaction with change of chemical bonds coupled to electron transfer","Free energy computation of reaction with change of chemical bonds coupled to electron transfer","館山 佳尚","館山 佳尚","Friday seminar, Centre for Computational Chemistry","Friday seminar, Centre for Computational Chemistry","2007-01-26","","jpn","oral_presentation","","","","","","","Reactions with electron transfer in solution, so called “redox reactions”, play crucial roles in a lot of interesting phenomena such as battery, fuel cell, catalysis, corrosion, photosynthesis. Fundamental quantities of redox reactions (redox potential, rate constant, current density etc.) are usually described by free energies. Therefore, computational methods that can quantitatively deal with free energy difference are quite desirable. On this issue, we have recently developed some new first-principles molecular dynamics (FPMD) techniques. Among them, we introduce the technique using the constrained FPMD method for quantitative discussion of electron transfer reactions with bond cleavage/formation." "Ab initio molecular dynamics study on free energies of electron and proton transfers in aqueous solution","水溶液中の電子・プロトン移動反応の第一原理自由エネルギー解析","館山 佳尚","館山 佳尚","第5回水素量子アトミクス研究会","第5回水素量子アトミクス研究会","2007-01-10","","jpn","oral_presentation","","","","","","","我々は酸化還元反応の定量的記述に向けた新しい第一原理自由エネルギー計算手法の開発に取り組み、これまでに幾つかの手法について実証に成功した。本講演では電子移動を伴う化学反応(例えば A + B + e- --> AB-)に向けて最近開発したBlue moon ensemble法を用いた計算手法について簡単に紹介する。" "溶液中の酸化還元反応の自由エネルギー解析に向けた第一原理MD手法の開発","溶液中の酸化還元反応の自由エネルギー解析に向けた第一原理MD手法の開発","館山 佳尚","館山 佳尚","物性研究所短期研究会「計算物性科学におけるスーパーコンピュータ利","物性研究所短期研究会「計算物性科学におけるスーパーコンピュータ利","2006-12-11","","jpn","oral_presentation","","","","","","","酸化還元反応は燃料電池、光触媒、光合成をはじめとする多くの興味深い現象の素過程である。 このような酸化還元反応の基本的物理量である様々な種類の自由エネルギーを密度汎関数理論ベースの分子動力学を用いて計算する手法の開発及び実証を行った。" "Coherent Phonon in Graphite under High-Density Photoexcitation","Coherent Phonon in Graphite under High-Density Photoexcitation","MOMIDA, Hiroyoshi, TATEYAMA, Yoshitaka, OHNO, Takahisa","MOMIDA, Hiroyoshi, TATEYAMA, Yoshitaka, OHNO, Takahisa","International Conference on Quantum Simulators and Design","International Conference on Quantum Simulators and Design","2006-12-03","","eng","oral_presentation","","","","","","We have investigated the effects of high density photo-excitation on the potential surface in graphite by using the first-principles electronic structure calculations, and examined possible reason for two peaks of the phonon frequencies observed by Ishioka et al. by using the ultra-fast pump-probe reflectivity measurements. Calculated results indicate a symmetry lowering of the structure and/or an anharmonicity of the potential energy surface, showing that the results possibly account for observed two-peaks structure.","" "First-principles MD techniques for free energy analysis of chemical reactions with electron transfer in solution","First-principles MD techniques for free energy analysis of chemical reactions with electron transfer in solution","館山 佳尚, Jochen Blumberger, 大野 隆央, Michiel Sprik","館山 佳尚, Jochen Blumberger, 大野 隆央, Michiel Sprik","International Conference on Quantum Simulators and Design","International Conference on Quantum Simulators and Design","2006-12-03","","jpn","oral_presentation","","","","","","","Reactions with electron transfer in solution, so called “redox reactions”, play crucial roles in a lot of interesting phenomena such as battery, fuel cell, catalysis, corrosion, photosynthesis. Fundamental quantities of redox reactions (redox potential, rate constant, current density etc.) are usually described by free energies. Therefore, computational methods that can quantitatively deal with free energy difference are quite desirable. On this issue, we have recently developed some new first-principles molecular dynamics (FPMD) techniques. Among them, we introduce the technique using the constrained FPMD method for quantitative discussion of electron transfer reactions with bond cleavage/formation." "First-principles MD techniques for free energy analysis of redox reactions in solution","First-principles MD techniques for free energy analysis of redox reactions in solution","館山 佳尚","館山 佳尚","Tne 9th Asian Workshop on First-Principles Electronic Structure ","Tne 9th Asian Workshop on First-Principles Electronic Structure ","2006-11-06","","jpn","oral_presentation","","","","","","","溶液中の電子・プロトン移動反応すなわち酸化還元反応は多くの興味深い現象ー燃料電池、電気分解、触媒、光合成ーの重要な素過程となっている。これらの反応の基本的な物理量は原理的にGibbs/Helmholtz自由エネルギーで記述される。従って電子数が一定で、内部(全)エネルギーを対象とする従来の第一原理計算では原理的に取扱いが困難であった。そこで我々は酸化還元反応の記述に向けた新しい第一原理自由エネルギー計算手法の開発・実証に取り組んだ。本講演では電子移動を伴う化学反応(例えば A + B + e- --> AB-)に向けて最近開発したBlue moon ensembleを用いた手法について説明した後、遷移金属錯体イオンによる水解離反応に適用した例を紹介する。" "TDDFTの実時間発展形式を用いた分子系の光励起状態の電子ー核ダイナミクス","TDDFTの実時間発展形式を用いた分子系の光励起状態の電子ー核ダイナミクス","館山 佳尚, 小山 紀久, 大野 隆央, 宮本良之","館山 佳尚, 小山 紀久, 大野 隆央, 宮本良之","分子構造総合討論会2006","分子構造総合討論会2006","2006-09-20","","jpn","oral_presentation","","","","","","","電子ー原子核ダイナミクスに向けて我々が開発・導入したRTP-TDDFTベースの 手法・技術について紹介し、さらに固体ベンゼンの光誘起環開裂への適用による実証計算に ついて報告する。" "Photoexcitation induced electron-nucleus dynamics by Real-Time Propagation (RTP) TDDFT","Photoexcitation induced electron-nucleus dynamics by Real-Time Propagation (RTP) TDDFT","館山 佳尚, 小山 紀久, 大野 隆央, 宮本良之","館山 佳尚, 小山 紀久, 大野 隆央, 宮本良之","Time dependent Density-Functional Theory: Prospects and Applicat","Time dependent Density-Functional Theory: Prospects and Applicat","2006-08-27","","jpn","oral_presentation","","","","","","","With the viewpoint of evaluating the ability of the real-time propagtion scheme of time-dependent density functional theory, we have examined prototypes of photoinduced structural transformations: The photoinduced ring-opening transformation in crystalline benzene and the trans-cis photoisomerisation of azobenzene molecule." "Free energy computation of redox reaction in aqueous solution via density-functional based ab initio molecular dynamics","第一原理MDによる酸化還元反応の自由エネルギー計算","館山 佳尚","館山 佳尚","大規模・高精度電子状態計算手法に関する研究会","大規模・高精度電子状態計算手法に関する研究会","2006-07-13","","jpn","oral_presentation","","","","","","","酸化還元反応の記述に向けた新しい第一原理自由エネルギー計算手法である、グランドカノニカル第一原理分子動力学法と第一原理分子動力学+エネルギーギャップ関係式についてその手法と精度実証について報告する。" "Photoexcitation induced electron-nucleus dynamics by real-time propagation TDDFT(RTP-TDDFT)","Photoexcitation induced electron-nucleus dynamics by real-time propagation TDDFT(RTP-TDDFT)","館山 佳尚, 小山 紀久, 大野 隆央, 宮本良之","館山 佳尚, 小山 紀久, 大野 隆央, 宮本良之","Symposium on Progress and Future Prospects in Molecular .....","Symposium on Progress and Future Prospects in Molecular .....","2006-06-06","","jpn","oral_presentation","","","","","","","With the viewpoint of evaluating the ability of this RTP-TDDFT scheme, we have examined prototypes of photoinduced structural transformations: The photoinduced ring-opening transformation in crystalline benzene and the trans-cis photoisomerisation of azobenzene molecule. " "Photoexcitation induced electron-ion dynamics by real-time propagation TDDFT","Photoexcitation induced electron-ion dynamics by real-time propagation TDDFT","館山 佳尚, 小山 紀久, 大野 隆央, 宮本良之","館山 佳尚, 小山 紀久, 大野 隆央, 宮本良之","CECAM workshop: New developments for first principles ...","CECAM workshop: New developments for first principles ...","2006-05-15","","jpn","oral_presentation","","","","","","","Using a formalism based on the real-time propagation time-dependent density functional theory (RTP-TDDFT), we have invesitgated the mechanisms of the photoinduced structural transformations of molecular systems on the femtosecond scale. We have shown for the first time that our method well reproduces the vibration frequencies in the excited state. This indicates the adequate accuracy of our method with respect to the shape of the excited-state PES." "Free energy analysis of electron and proton transfer reactions in solution via first-principles MD","溶液中の電子・プロトン移動反応に対する第一原理自由エネルギー解析","館山 佳尚","館山 佳尚","東京大学物性研究所 理論セミナー","東京大学物性研究所 理論セミナー","2006-05-12","","jpn","oral_presentation","","","","","","","溶液中の電子・プロトン移動反応すなわち酸化還元反応は多くの興味深い現象ー燃料電池、電気分解、腐食、触媒、光合成ーの重要な素過程となっている。これらの反応の基本的な物理量は原理的にGibbs/Helmholtz自由エネルギーで記述される。従って電子数が一定で、内部(全)エネルギーを中心とする従来の第一原理計算では原則取扱いが困難となっている。 そこで我々は酸化還元反応の記述に向けた新しい第一原理自由エネルギー計算手法の開発・実証に取り組んできた。本講演ではそれらの手法論及び水溶液中の遷移金属錯体系を用いた精度検証について報告する。" "Free energy analysis of electron and proton transfer reactions in solution via first-principles MD","溶液中の電子・プロトン移動反応に対する第一原理自由エネルギー解析","館山 佳尚","館山 佳尚","物性研究所客員所員講演会","物性研究所客員所員講演会","2006-04-20","","jpn","oral_presentation","","","","","","","第一原理分子動力学法を用いた電子移動及びプロトン移動反応に関する自由エネルギー計算についての私の最近の取り組みを報告する。" "PHOTOEXCITATION INDUCED ELECTRON-ION DYNAMICS BY REAL-TIME PROPAGATION TDDFT (RTP-TDDFT) ","PHOTOEXCITATION INDUCED ELECTRON-ION DYNAMICS BY REAL-TIME PROPAGATION TDDFT (RTP-TDDFT) ","館山 佳尚, 小山 紀久, 大野 隆央, 宮本良之","館山 佳尚, 小山 紀久, 大野 隆央, 宮本良之","CSW2006","CSW2006","2006-04-17","","jpn","oral_presentation","","","","","","","With the viewpoint of evaluating the ability of this RTP-TDDFT scheme, we have examined prototypes of photoinduced structural transformations: The photoinduced ring-opening transformation in crystalline benzene and the trans-cis photoisomerisation of azobenzene molecule. " "実時間発展TDDFTを用いた分子の光励起状態の電子ー核ダイナミクス","実時間発展TDDFTを用いた分子の光励起状態の電子ー核ダイナミクス","館山 佳尚, 小山 紀久, 大野 隆央, 宮本良之","館山 佳尚, 小山 紀久, 大野 隆央, 宮本良之","日本物理学会第61回年次大会","日本物理学会第61回年次大会","2006-03-27","","jpn","oral_presentation","","","","","","","時間依存密度汎関数理論(TDDFT)を時間ドメインで取扱う実時間発展(RTP)-TDDFTは、光励起状態の電子ー核ダイナミクスの解析への応用が期待されているが、その中で用いられている様々な 近似の妥当性については不明な点が数多く残っている。我々は光励起状態での分子振動数や励起緩和時間の解析を行うことにより、RTP-TDDFTを基にした我々のスキームが定量的解析に適用可能であることを実証した。" "第一原理オーダーN手法の開発とナノ物質への応用","第一原理オーダーN手法の開発とナノ物質への応用","大野 隆央, 宮崎 剛, 木野 日織, 西野 正理, 奈良 純, 館山 佳尚, 尾崎 泰助","大野 隆央, 宮崎 剛, 木野 日織, 西野 正理, 奈良 純, 館山 佳尚, 尾崎 泰助","科研費特定領域研究「量子デザイン手法の開発」第1回研究報告会","科研費特定領域研究「量子デザイン手法の開発」第1回研究報告会","2006-03-10","","jpn","oral_presentation","","","","","","","科研費特定領域研究「次世代量子シミュレータ・量子デザイン手法の開発と応用」のA02班、大野班の平成17年度の研究成果を紹介する。特に、Ge/Si(001)系に対するオーダーN法第一原理計算の結果と現状を説明する。" "New ab-initio MD methods for redox (electron transfer) reaction in solution","溶液中の酸化還元(電子移動)反応解析に向けた新しい第一原理分子動力学手法","館山 佳尚","館山 佳尚","生物物理化学理論研究室講演会","生物物理化学理論研究室講演会","2006-02-01","","jpn","oral_presentation","","","","","","","酸化還元反応は多くの興味深い現象ー腐食、(燃料)電池、触媒、光合成などーの重要な素過程となっている。しかし酸化還元反応の諸物理量ー酸化還元電位などーを第一原理的に計算する手法は今までなかった。この問題に対し、我々は最近2つの新しい第一原理分子動力学手法ー「grand-canonical DF-MD」及び「DF-MD +Marcus energy gap law」ーを開発し、その有効性を確認した。本講演ではその手法論及び水溶液中の遷移金属錯体系を用いた精度検証について報告する。" "Redox reactions in aqueous solution by new ab-initio molecular dynamics methods","新規第一原理計算手法による水溶液中の酸化還元反応解析","館山 佳尚, J. Blumberger, M. Sprik, 大野 隆央","館山 佳尚, J. Blumberger, M. Sprik, 大野 隆央","東京大学物性研究所短期研究会「固体における水素の科学」","東京大学物性研究所短期研究会「固体における水素の科学」","2005-11-24","","jpn","oral_presentation","","","","","","","水溶液中での水分子の解離が絡んだ遷移金属錯体の酸化還元反応に対して、我々が開発した酸化還元反応向けの新規第一原理計算手法を用いて行った解析について、手法論を交えながら報告する。" "Grand-canonical density-functional molecular-dynamics study on redox reactions of aqueous transition-metal complexes","Grand-canonical density-functional molecular-dynamics study on redox reactions of aqueous transition-metal complexes","館山 佳尚","館山 佳尚","電極/溶液系の計算科学研究会","電極/溶液系の計算科学研究会","2005-11-24","","jpn","oral_presentation","","","","","","","Thermochemistry of the redox reactions of anionic transition metal complexes in aqueous solution is studied by the grand-canonical density functional molecular dynamics method recently developed. We found that typical error in the standard redox potentials is estimated to be around 0.2 eV even in a small supercell, indicating that this theoretical approach is promising for the further application" "Real-time propagation time-dependent density functional study on photoexcitation-induced electron-ion dynamics","Real-time propagation time-dependent density functional study on photoexcitation-induced electron-ion dynamics","館山 佳尚","館山 佳尚","電子相関と電子励起に関する研究会","電子相関と電子励起に関する研究会","2005-11-21","","jpn","oral_presentation","","","","","","","Photoexcitation-induced electron-ion dynamics is investigated by means of a computational method based on real-time propagation (RTP) time-dependent density functional theory (TDDFT). The vibrational analysis in the excited states indicates that our method is adequately accurate." "New density-functional molecular dynamics methods for redox reaction in solution","溶液中の酸化還元反応解析のための新しい第一原理MD手法の開発","館山 佳尚, Michiel Sprik, 大野 隆央","館山 佳尚, Michiel Sprik, 大野 隆央","第28回溶液化学シンポジウム","第28回溶液化学シンポジウム","2005-11-17","","jpn","oral_presentation","","","","","","","我々は電子系に対してgrand-canonical形式を適用した化学ポテンシャル一定の第一原理MD手法及びMarcus電子移動理論のエネルギーギャップ関係式への第一原理MDの適用という2つの新しいアプローチが、共に水溶液中の酸化還元反応の諸物理量を比較的良い精度で計算可能であることを示した。" "Grand-canonical DFT-MD法及びDFT-MD+Marcus energy gap法による水溶液中の酸化還元反応の解析","Grand-canonical DFT-MD法及びDFT-MD+Marcus energy gap法による水溶液中の酸化還元反応の解析","館山 佳尚, Michiel Sprik, 大野 隆央","館山 佳尚, Michiel Sprik, 大野 隆央","分子構造総合討論会2005","分子構造総合討論会2005","2005-09-27","","jpn","oral_presentation","","","","","","","酸化還元反応は多くの興味深い現象ー腐食、(燃料)電池、触媒、 光合成などーの重要な素過程となっている。しかし酸化還元反応の 諸物理量ー酸化還元電位などーを第一原理的に計算する手法は今ま でなかった。この問題に対し、我々は最近2つの新しい第一原理分 子動力学手法ー「grand-canonical DF-MD」及び「DF-MD + Marcus のエネルギーギャップ則」ーを開発し、その有効性を確認した。 本講演では手法論及び水溶液中の遷移金属" "TDDFTの実時間発展形式による光異性化のフェムト秒ダイナミクスの理論的研究","TDDFTの実時間発展形式による光異性化のフェムト秒ダイナミクスの理論的研究","小山 紀久, 館山 佳尚, 宮本良之, 大野 隆央, 大野隆央","小山 紀久, 館山 佳尚, 宮本良之, 大野 隆央, 大野隆央","分子構造討論会","分子構造討論会","2005-09-27","","jpn","oral_presentation","","","","","","","分子スイッチなどのナノデバイスの実用化が現実性を帯びる中、フェムト秒オーダーの光化学反応を記述する理論的計算手法の開発は重要なテーマである。我々は時間依存密度汎関数理論(TD-DFT)に基づく実時間発展計算により、超高速光化学反応の電子-イオンのダイナミクスを計算する手法を開発した。我々の手法では波動関数の実時間発展を4次のSuzuki-Trotter分解を利用して計算することによって、高精度で安定した長時間シミュレーションの実現を可能にしている。この手法を長年議論になっているトランスアゾベンゼンの光異性化反応に適用し、これまでの実験結果とつじつまのあう興味深い結果が得られたので報告する。" "時間依存密度汎関数理論によるアゾベンゼンの光異性化メカニズムの解明","時間依存密度汎関数理論によるアゾベンゼンの光異性化メカニズムの解明","小山 紀久, 館山 佳尚, 宮本良之, 大野 隆央","小山 紀久, 館山 佳尚, 宮本良之, 大野 隆央","光化学討論会","光化学討論会","2005-09-12","","jpn","oral_presentation","","","","","","","分子スイッチなどのナノデバイスにおいて最も基本的なトランスアゾベンゼンに注目し、時間依存密度汎関数理論(TD-DFT)に基づく第一原理計算によってその光異性化メカニズムを検討した。まずS1励起に関しては励起直後からN=Nボンド周りでねじれを生じ、これまでのコンセンサスとは異なる回転メカニズムに従って異性化が進行することが明らかとなった。一方、S2励起に関しては励起後も構造は平坦性を維持するものの電子状態が不安定となり、遅くとも100フェムト秒までにはS1状態へ非断熱遷移を起こし、S1状態を介してシス体へ異性化することが明らかとなった。" "Grand canonical CMD method and the energy gap formulation for redox potential: A study of anionic redox reeactions in aqueous so","Grand canonical CMD method and the energy gap formulation for redox potential: A study of anionic redox reeactions in aqueous so","館山 佳尚","館山 佳尚","CPMD2005","CPMD2005","2005-09-03","","jpn","oral_presentation","","","","","","","We compare the results of a recently developed grand canonical CPMD method for the computation of oxidation free energy (redox potential) to the energy gap formulation based on Marcus theory of electron transfer. We found that the calculated redox potentials are in good agreement between both methods in the redox reactions of anionic transition metal complexes, to which Marcus theory can be assumed to apply. Compared to the experimental values, the typical error of the grand canonical method is estimated to be around 0.2 eV in the periodic box with 30 water molecules. The size effects, in response to increasing the number of water from 30 to 48, are found to be small (~0.1 eV) in the present reactions. The link to Marcus theory also enables us to compute reorganization free energy for oxidations. These two methods may give an insight into the reorganization of the solute and solvent motions in electron transfer reactions as well." "グランドカノニカル第一原理MDとMarcusのエネルギーギャップ関係式による水溶液中の酸化還元反応の考察","グランドカノニカル第一原理MDとMarcusのエネルギーギャップ関係式による水溶液中の酸化還元反応の考察","館山 佳尚","館山 佳尚","つくば計算物質生命科学コロキウム","つくば計算物質生命科学コロキウム","2005-06-10","","jpn","oral_presentation","","","","","","","我々はグランドカノニカル形式を用いた化学ポテンシャル一定の 第一原理MD手法及びMarcusの電子移動理論で導出されるエネルギー ギャップ関係式への第一原理MDの適用という2つの新しいアプローチ についてその有効性の検討を行った。テスト系としては水溶液中の イオン原子・分子に関する酸化還元反応を使用した。まず標準酸化還元電位に ついては小さなユニットセルでも比較的良い精度(~0.2 eV程度のエラー)が 得られることが示された。一方再配置エネルギーについてはサイズ効果が 大きいだろうという兆候が見つかった。またこれらの結果の解析の中で、 両アプローチの間に一定の関係があることを見いだした。講演では 両アプローチの手法論を中心にその検討過程の詳細について報告する。" "グランドカノニカル第一原理MDとエネルギーギャップ関係式による水溶液中の酸化還元反応の考察","グランドカノニカル第一原理MDとエネルギーギャップ関係式による水溶液中の酸化還元反応の考察","館山 佳尚","館山 佳尚","青木・常行研コロキウム","青木・常行研コロキウム","2005-05-12","","jpn","oral_presentation","","","","","","","我々はgrand canonical形式を用いた第一原理MD手法及び Marcusの電子移動理論を基に導出されるエネルギーギャップ 関係式への第一原理MDの適用という2つの新しいアプローチ から水溶液中の酸化還元反応の諸物理量を求め、各々の アプローチの有効性について検討を行った。例えば標準酸化 還元電位については比較的小さなユニットセルでも良い精度が 得られることが示された。これらの手法は電極・溶液・生体 反応への応用が大いに期待できる。" "アゾベンゼンの光異性化メカニズムに関する理論的研究","アゾベンゼンの光異性化メカニズムに関する理論的研究","小山 紀久, 館山 佳尚, 宮本良之, 大野 隆央","小山 紀久, 館山 佳尚, 宮本良之, 大野 隆央","日本化学会第85春季年会","日本化学会第85春季年会","2005-03-26","","jpn","oral_presentation","","","","","","","時間依存密度汎関数理論に基づき、トランスアゾベンゼンの励起後のダイナミクスを計算し、長年未解決である光異性化メカニズムに関して検討した。その結果、S1励起に関しては励起直後からN=Nボンドがねじれ、これまで長年信じられてきた反転メカニズムではなく、回転メカニズムに従って異性化が進行することが明らかとなった。これはねじれによってp軌道成分が増加するHOMOと、s軌道成分が増加するLUMOに電子がそれぞれ存在するするため、結果として90°程度ねじれた方がエネルギー的に安定となるためである。一方、S2励起に関しては励起直後から電子状態が不安定となり、構造は平坦性を維持し続けた。また100フェムト秒程度でS1状態へ遷移し、直接基底状態のcis体へ遷移することはないことが明らかとなった。" "Constant chemical potenital Car-Parrinello MD study on redox reactions in aqueous solution","化学ポテンシャル一定の第一原理MDによる水溶液中の電子移動反応の解析","館山 佳尚, Michiel Sprik","館山 佳尚, Michiel Sprik","日本物理学会第60回年次大会","日本物理学会第60回年次大会","2005-03-24","","jpn","oral_presentation","","","","","","","水溶液中の原子・分子の酸化還元反応に対して、グランドカノニカルカーパリネロ分子動力学法を適用し、標準酸化還元電位の見積もりを行った。さらに溶媒効果など個々の寄与の検討を通して、自由エネルギー差に対する本計算手法の精度について吟味を行った。また既存の電子移動反応理論との関連性についても新しい知見を得た。" "Dynamics of the photoisomerization process of trans-azobenzene: A time-dependent density functinal study","Dynamics of the photoisomerization process of trans-azobenzene: A time-dependent density functinal study","小山 紀久, 館山 佳尚, 宮本良之, 大野 隆央","小山 紀久, 館山 佳尚, 宮本良之, 大野 隆央","Annual APS March Meeting 2005","Annual APS March Meeting 2005","2005-03-21","","jpn","oral_presentation","","","","","","","Azobenzene is a typical molecule which shows a reversible photoisomerization, and has attractive considerable attention for molecular devices. The photoisomerization mechanism of trans-azobenzene, however, has been controversial for over a half century because of its ultra-fast reaction. In this work, we investigated the dynamics of the photoisomerization process of trans-azobenzene based on time-dependent density functional theory. Our calculations clearly indi-cate that the photoisomerization process for S$_1$ excitation occurs through a rotation channel against the widely-accepted inversion mechanism. In contrast, it was found that a direct isomeriza-tion does not occur for S$_2$ excitation, and a transition to S$_1$ occurs at about 100fs." "H-INDUCED DECOHESION ACROSS THE GRAIN BOUNDARY AND H-ENHANCED VACANCY ACTIVITY IN METALS","H-INDUCED DECOHESION ACROSS THE GRAIN BOUNDARY AND H-ENHANCED VACANCY ACTIVITY IN METALS","耿 文通, Arthur J. Freeman, Gregory B. Olson, 館山 佳尚, 大野 隆央","耿 文通, Arthur J. Freeman, Gregory B. Olson, 館山 佳尚, 大野 隆央","The 11th International Conference on Fracture","The 11th International Conference on Fracture","2005-03-20","","jpn","oral_presentation","","","","","","","The rapid diffusion of H in metals permits an easy segregation to the grain boundary and an easy trapping to the vacancy. H-induced intergranular embrittlement in metals such as Fe and Ni is generally a result of coalition of segregated H and other embrittling impurities at the grain boundary. Ab initio total energy calculations based on the density functional theory have shown that H alone can also weaken the cohesion across the grain boundary. The stronger binding of H with a free surface than with a grain boundary, which results in grain boundary embrittlement according to the Rice-Wang theory, can be ascribed to its monovalency. New tensile experiments point to a H-enhanced vacancy contribution to the increased susceptibility of steel to H embrittlement. Ab initio calculations on the energetics of interstitial H, vacancy, and H-monovacancy complexes (VHn) in Fe have shown that the predominant complex under ambient condition of H pressure is VH2, not VH6 as previously suggested by effective-medium theory c" "Electrochemistry in a very small cell: A computational approach","Electrochemistry in a very small cell: A computational approach","Michiel Sprik, Jochen Blumberger, 館山 佳尚","Michiel Sprik, Jochen Blumberger, 館山 佳尚","The 229th ACS National Meeting","The 229th ACS National Meeting","2005-03-13","","jpn","oral_presentation","","","","","","","Electrochemists control the thermodynamic driving force of redox reactions in an electrochemical cell by applying a voltage to the electrodes. In computations the same effect can be achieved by shifting the potential energy surfaces of different oxidations states with respect to each other (omitting any physical electrode). We have implemented this method using density functional theory based ab initio molecular dynamics simulation ("Car-Parrinello"). In this talk we summarize the latest results we have obtained applying this method to a number of small redox active aqueous solutes (mainly transition metal complexes). We compare our computations to experiment (redox potentials) as well as theory (Marcus Theory of electron transfer.)" "Real time dynamics of photoinduced deformation in solid benzene by TDDFT","Real time dynamics of photoinduced deformation in solid benzene by TDDFT","館山 佳尚, 宮本良之, 小山 紀久, 大野 隆央","館山 佳尚, 宮本良之, 小山 紀久, 大野 隆央","Time dependent Density-Functional Theory: Prospects and Applicat","Time dependent Density-Functional Theory: Prospects and Applicat","2004-09-07","","jpn","oral_presentation","","","","","","","Coupled dynamics of ions and electrons in the excited states of molecular and solid benzene is investigated on the femtosecond scale by TDDFT with the Suzuki-Trotter decomposition for the propagation. Within the $pi$ - $pi^*$ excitations, any out-of-plane motion of the ions is not induced in the molecular system, as expected from the symmetry consideration. In the solid, however, we found that large swing of the C-H bonds and subsequent twist of the carbon ring take place, leading to $sp3$-like bonding of carbon ions. This swing-to-twist motion presents a plausible mechanism underlying the photoinduced ring opening in solid benzene experimentally observed under pressure." "Fist-principles/Tight-binding hybrid simulation for Si system","Si系の第一原理/強結合ハイブリッド計算","中村 美道, 高橋 憲彦, 高木祥光, 宇田毅, 西川宜孝, 新田仁, 館山 佳尚, 大野 隆央","中村 美道, 高橋 憲彦, 高木祥光, 宇田毅, 西川宜孝, 新田仁, 館山 佳尚, 大野 隆央","日本物理学会 第59回年次大会","日本物理学会 第59回年次大会","2004-03-27","","jpn","oral_presentation","","","","","","","Si系での応用を念頭に第一原理(FP)/強結合(TB)ハイブリッド計算手法を開発した。手法の有効性、および今後の応用について紹介する。" "Time-dependent density functional study on the photoisomerization mechanism of azobenzene","Time-dependent density functional study on the photoisomerization mechanism of azobenzene","小山 紀久, 館山 佳尚, 宮本良之, 大野 隆央","小山 紀久, 館山 佳尚, 宮本良之, 大野 隆央","Annual APS March Meeting 2004","Annual APS March Meeting 2004","2004-03-22","","jpn","oral_presentation","","","","","","","Photochemical reactions in organic molecules have attracted considerable attention in semiconductor physics and also in bioscience. Azobenzene is a simple molecule which shows the reversible photoisomerization at high quantum yields, and can be used as a light-driven molecular switch and so on. However, the photoisomerization process of azobenzene is still an open question because of its femtosecond ultra-fast reaction. In this talk, we present time-dependent density functional calculations for the azobenzene molecule, and discuss the mechanism of photoisomerization induced by S1 and S2 excitations. This research is partially supported by ACT-JST, and also by FSIS and Special Coordination Funds of MEXT of Japanese Government. The calculations were carried out partly using the Numerical Materials Simulator in National Institute for Materials Science, and partly using the NEC-SX5 at Cybermedia Center of Osaka University." "TDDFT-MD Study on Dynamics in Photoinduced Ring Opening of Benzene","TDDFT-MD Study on Dynamics in Photoinduced Ring Opening of Benzene","大野 隆央, Y.Miyamoto, 小山 紀久, 館山 佳尚","大野 隆央, Y.Miyamoto, 小山 紀久, 館山 佳尚","Annual APS March Meeting 2004","Annual APS March Meeting 2004","2004-03-22","","jpn","oral_presentation","","","","","","","ベンゼン結晶は光照射下で通常より低い圧力で開環反応を伴う構造変化を引き起こす。時間依存密度汎関数法を用いて、光照射による電子励起下でのベンゼン環の構造変化を解析した。その結果、ベンゼン分子では開環反応は起こらないが、結晶中では分子間の相互作用により開環反応が誘起される可能性があることを見出した。"