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

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.

Electronic Transport Properties of Molecular Clusters Sb4O6, P4Se3, and P4O6

“…The CTI helps explain the transfer of charge carriers through atomic orbitals between atoms and clusters in order to shed light on the electronic transport in the materials. The probability and efficiency of charge hopping events are calculated using CTI in order to explore the electrical connection between the structural units in IMCs. ,, The mechanism of carrier hopping in the framework of charge transport can expeditiously describe the transfer of charge carriers from one site to another in the materials across interfaces or the molecular crystals. − The transfer of charge carriers between electron donor and acceptor sites involves the overlapping of atomic or molecule orbitals in the electronic materials. − The rate and effectiveness of charge hopping events are primarily determined by the CTI as it helps in determining the degree of electronic connection between the initial and final states involved in the electronic transitions. The probability as well as the rate of charge transfer and carrier mobility are directly impacted by the CTI outcomes.…”