Quantum Rate Theory and Electron-Transfer Dynamics: A Theoretical and Experimental Approach for Quantum Electrochemistry

TL;DR

This paper introduces a quantum rate theory linking quantum electrodynamics and electron transfer, validated through experiments on molecular films, offering new insights into quantum electrochemistry.

Contribution

It presents a novel quantum rate theory based on first principles that integrates quantum electrodynamics with electron transfer dynamics, validated experimentally.

Findings

Quantum rate theory describes electron transfer with quantum capacitance.

The theory explains quantum conductance and capacitance in molecular films.

Validation shows agreement with experimental electron transfer data.

Abstract

Quantum rate theory is based on a first-principle quantum mechanical rate concept that comprises with the Planck-Einstein relationship $E = h\nu$, where $\nu = e^2/hC_q$ is a frequency associated with the quantum capacitance $C_q$ and $E = e^2/C_q$ is the energy associated with $\nu$. For a single state mode of transmittance, $e^2/C_q$ corresponds to the chemical potential differences $\Delta \mu$ between donor and acceptor state levels comprising an electrochemical reaction. The latter assumption implies quantum electrodynamics within a particular quantum transport mode intrinsically coupled to the electron-transfer rate of electrochemical reactions that have not been considered thus far. Here it is demonstrated that the consideration of this inherent quantum transport is key to obtaining an in-depth understanding of the electron transfer phenomenon. Finally, the theory is validated through its description of electron transfer, quantum conductance, and capacitance in different electro-active molecular films.