The structure and electronic properties of a molecule at an electrochemical interface are changed by interactions with the electrode surface and the electrolyte solution, which can be significantly modulated by an applied voltage. We present an efficient self-consistent quantum mechanics/molecular mechanics (QM/MM) approach to study a physisorbed molecule at a metal electrode–electrolyte interface under the constant-voltage condition. The approach employs a classical polarizable double electrode model, which enables us to study the QM/MM system in the constant-voltage ensemble. A mean-field embedding approximation is further introduced in order to overcome the difficulties associated with statistical sampling of the electrolyte configurations. The results of applying the method to a test system indicate that the adsorbed molecule is no less or slightly more polarized at the interface than in the bulk electrolyte solution. The geometry of the horizontally adsorbed molecule is modulated by their electrostatic interactions with the polarizable electrode surfaces and also the interactions with cations attracted toward the interface when the adsorbate is reduced. We also demonstrate that the approach can be used to quantitatively evaluate the reorganization energy of a one electron reduction reaction of a molecule in an electrochemical cell.
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Accelerated constant-voltage quantum mechanical/molecular mechanical method for molecular systems at electrochemical interfaces
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21 December 2022
Research Article|
December 16 2022
Accelerated constant-voltage quantum mechanical/molecular mechanical method for molecular systems at electrochemical interfaces
Special Collection:
JCP Editors' Choice 2022
Ken Takahashi
;
Ken Takahashi
(Data curation, Formal analysis, Investigation, Methodology, Software, Visualization, Writing – original draft, Writing – review & editing)
1
Department of Molecular Engineering, Kyoto University
, Kyoto Daigaku Katsura, Kyoto 615-8246, Japan
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Hiroshi Nakano
;
Hiroshi Nakano
a)
(Conceptualization, Formal analysis, Funding acquisition, Investigation, Methodology, Project administration, Resources, Software, Supervision, Validation, Writing – original draft, Writing – review & editing)
2
CD-FMat, National Institute of Advanced Industrial Science and Technology (AIST)
, 1-1-1 Umezono, Tsukuba Central 2, Tsukuba, Ibaraki 305-8568, Japan
a)Author to whom correspondence should be addressed: h.nakano@aist.go.jp
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Hirofumi Sato
Hirofumi Sato
(Funding acquisition, Project administration, Resources, Supervision, Writing – review & editing)
1
Department of Molecular Engineering, Kyoto University
, Kyoto Daigaku Katsura, Kyoto 615-8246, Japan
3
Fukui Institute for Fundamental Chemistry, Kyoto University
, Takano Nishihiraki-cho 34-4, Sakyo-ku, Kyoto 606-8103, Japan
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a)Author to whom correspondence should be addressed: h.nakano@aist.go.jp
J. Chem. Phys. 157, 234107 (2022)
Article history
Received:
September 28 2022
Accepted:
December 01 2022
Citation
Ken Takahashi, Hiroshi Nakano, Hirofumi Sato; Accelerated constant-voltage quantum mechanical/molecular mechanical method for molecular systems at electrochemical interfaces. J. Chem. Phys. 21 December 2022; 157 (23): 234107. https://doi.org/10.1063/5.0128358
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