Electron Transfer at Molecule–Metal Interfaces under Floquet Engineering: Rate Constant and Floquet Marcus Theory

IF 3.7 Q2 CHEMISTRY, PHYSICAL ACS Physical Chemistry Au Pub Date : 2023-12-21 DOI:10.1021/acsphyschemau.3c00049
Yu Wang,  and , Wenjie Dou*, 
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Abstract

Electron transfer (ET) at molecule–metal or molecule–semiconductor interfaces is a fundamental reaction that underlies all electrochemical processes and substrate-mediated surface photochemistry. In this study, we show that ET rates near a metal surface can be significantly manipulated by periodic driving (e.g., Floquet engineering). We employ the Floquet surface hopping and Floquet electronic friction algorithms developed previously to calculate the ET rates near the metal surface as a function of driving amplitudes and driving frequencies. We find that ET rates have a turnover effect when the driving frequencies increase. A Floquet Marcus theory is further formulated to analyze such a turnover effect. We then benchmark the Floquet Marcus theory against Floquet surface hopping and Floquet electronic friction methods, indicating that the Floquet Marcus theory works in the strong nonadiabatic regimes but fails in the weak nonadiabatic regimes. We hope these theoretical tools will be useful to study ET rates in the plasmonic cavity and plasmon-assisted photocatalysis.

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Floquet 工程下分子-金属界面的电子转移:速率常数和 Floquet Marcus 理论
分子-金属或分子-半导体界面上的电子转移(ET)是一种基本反应,是所有电化学过程和基底介导的表面光化学的基础。在本研究中,我们发现金属表面附近的 ET 速率可以通过周期性驱动(如 Floquet 工程)得到显著控制。我们采用之前开发的 Floquet 表面跳跃和 Floquet 电子摩擦算法,计算出金属表面附近的 ET 率与驱动振幅和驱动频率的函数关系。我们发现,当驱动频率增加时,ET 率会产生周转效应。我们进一步提出了 Floquet Marcus 理论来分析这种周转效应。然后,我们将 Floquet Marcus 理论与 Floquet 表面跳跃法和 Floquet 电子摩擦法进行对比,结果表明 Floquet Marcus 理论在强非绝热状态下有效,但在弱非绝热状态下失效。我们希望这些理论工具将有助于研究质子腔和质子辅助光催化中的 ET 速率。
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期刊介绍: ACS Physical Chemistry Au is an open access journal which publishes original fundamental and applied research on all aspects of physical chemistry. The journal publishes new and original experimental computational and theoretical research of interest to physical chemists biophysical chemists chemical physicists physicists material scientists and engineers. An essential criterion for acceptance is that the manuscript provides new physical insight or develops new tools and methods of general interest. Some major topical areas include:Molecules Clusters and Aerosols; Biophysics Biomaterials Liquids and Soft Matter; Energy Materials and Catalysis
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