Atomistic understanding of the electrode potential effect on the electrochemical processes by the newly developed constant electrode potential QM/MM method

通过新开发的恒定电极电位 QM/MM 方法从原子角度理解电极电位对电化学过程的影响

• 批准号: 22KJ1854
• 负责人: 高橋 健
• 金额: $ 1.02万
• 依托单位: Kyoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for JSPS Fellows
• 财政年份: 2023
• 资助国家: 日本
• 起止时间: 2023-03-08 至 2024-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-22KJ1854/
• 关键词: 分子動力学シミュレーション; 電気化学; QM/MM法; 量子化学; 電極電解液界面; 微分容量

電気化学測定は、三極セルを用いて作用電極-参照電極間の電位差が一定に、すなわち作用電極の電位が絶対値的に一定なるように、作用電極-対極間の電位差を制御して行われる。2022年度はまず、古典分子動力学(MD)手法において絶対電位を制御した計算を行い、電極電解液界面挙動の電位依存性を調べた。三極測定実験と同様に、作用電極-対極間の電位差を自己無撞着的に決定することで、作用電極電位を0.1 V刻みで制御できることを示した。電位依存性のある物理量として電気二重層微分容量C(V)を計算した。金属電極の電子分極を司るパラメータを、従来の、電極を完全導体とした場合はC(V)は実験と定性的にも一致しない一方、量子化学(SCC-DFTB)計算の結果を再現するも のに変更することで、C(V)は増大し、ゼロ電荷電位(PZC)-0.2 Vで極大を示すようになる等、実験との一致が大幅に向上するこ とを示した。本成果は本報告書作成時点で論文としてChem. Phys. Lett.に投稿済み、査読中である。 次に、量子化学計算と古典MD法を組み合わせ、MM領域との相互作用を平均場的に量子化学計算に取り込むという近似(平均場近似)を加えたハイブリッド手法(平均場QM/MM法)に拡張した。QM分子としてグリシンを選び、その構造最適化計算を電位制御下で行えることを示した。結合角や結合長は電位変化に対して鈍感である一方、電極界面での電解質イオンの分布は電位に敏感に応答するため、それらとの相互作用を通してグリシンの電子分極は電位に敏感に応答することを示した。

For the determination of electrical chemistry, the use of electrodes, the use of electrodes in the determination of electrical chemistry, the use of electrodes, the use of electrodes, the use of electrodes in the determination of electrical chemistry, the use of electrodes in the determination of electrical chemistry, the use of electrodes in the determination of electrical potential, the use of electrodes in the determination of electrical potential, the use of electrodes in the measurement of electrical chemistry, the use of electrodes in the measurement of electrical chemistry, the use of electrodes in the determination of electrical potential, the use of electrodes in the determination of electrical potential, the use of electrodes in the determination of electrical potential, the use of electrodes In the year 2022, the classical molecular dynamics (MD) technique was used to determine the potential dependence of the interface between the electronic solution and the electronic hydrolysate. Three-pole determination of the same voltage, the determination of the potential difference between the two electrodes, the determination of the potential difference between the two electrodes, and the determination of the voltage difference between the electrodes and the electrodes. The electrode potential 0.1 V is used to control the temperature. Potential dependence, physical quantity, differential capacity C (V), double differential capacity, calculation and calculation. Metal electrons are responsible for the determination of carbon dioxide (C (V)). The results of quantum chemistry (SCC-DFTB) calculation show that the temperature difference is higher than that of normal temperature, C (V) high temperature, low charge potential (PZC)-0.2V high voltage, etc. The data are consistent with each other by a large margin. This paper reports on the completion time of this paper. This article is based on the Chem. Phys. Lett. In the course of contribution, the contribution is in progress. Quantum chemistry calculation of the average field of classical MD method and MM field interaction is based on the average field approximation (mean field approximation) plus the average field QM/MM method (mean field method). The QM molecule is used to select and optimize the calculation of the electronic potential system. Combined with the combination of the long-term electric potential, the distribution of the electrical potential, the distribution of the electrical potential, the interaction of the electrical potential, the electrical potential, the electric potential, the electric potential

项目成果

絶対電位制御MD法による電極界面の電位依存性の解析

使用绝对电位控制MD方法分析电极界面的电位依赖性

• 发表时间: 2022
• 作者: 高橋健;佐藤啓文;中農浩史
• 通讯作者: 中農浩史

Unified polarizable electrode models for open and closed circuits: Revisiting the effects of electrode polarization and different circuit conditions on electrode-electrolyte interfaces

开路和闭路的统一可极化电极模型：重新审视电极极化和不同电路条件对电极-电解质界面的影响

• DOI: 10.1063/5.0093095
• 发表时间: 2022
• 期刊: The Journal of Chemical Physics
• 作者: Takahashi Ken;Nakano Hiroshi;Sato Hirofumi
• 通讯作者: Sato Hirofumi

Classical polarizable MD simulation method for open circuit systems: Revisit of electrode polarization effect and Comparison of electrical double layer relaxation dynamics with closed circuit systems

开路系统的经典极化MD模拟方法：电极极化效应的回顾以及双电层弛豫动力学与闭路系统的比较

• 发表时间: 2022
• 作者: Ken Takahashi;Hiroshi Nakano;Hirofumi Sato
• 通讯作者: Hirofumi Sato

Accelerated constant-voltage quantum mechanical/molecular mechanical method for molecular systems at electrochemical interfaces

电化学界面分子系统的加速恒压量子力学/分子力学方法

• DOI: 10.1063/5.0128358
• 发表时间: 2022
• 期刊: The Journal of Chemical Physics
• 作者: Takahashi Ken;Nakano Hiroshi;Sato Hirofumi
• 通讯作者: Sato Hirofumi