# Electron transfer at thermally heterogeneous molecule-metal interfaces

## TL;DR

This paper develops a theoretical framework for electron transfer at molecule-metal interfaces with different local temperatures, revealing its connection to heat transfer and interfacial thermal conduction.

## Contribution

It introduces a bithermal Marcus formalism to describe electron transfer and heat transfer at temperature-heterogeneous interfaces, providing new analytical expressions and coupled dynamical equations.

## Key findings

- Electron transfer is linked to heat transfer across the interface.
- Electron exchange contributes to interfacial heat conduction even without net current.
- The formalism applies across various geometries and temperature gradients.

## Abstract

The rate of electron transfer between a molecular species and a metal, each at a different local temperature, is examined theoretically through implementation of a bithermal (characterized by two temperatures) Marcus formalism. Expressions for the rate constant and the electronic contribution to a heat transfer mechanism which is induced by the temperature gradient between molecule and metal are constructed. The system of coupled dynamical equations describing the electronic and thermal currents are derived and examined over diverse ranges of reaction geometries and temperature gradients. It is shown that electron transfer across the molecule-metal interface is associated with heat transfer and that the electron exchange between metal and molecule makes a distinct contribution to the interfacial heat conduction even when the net electronic current vanishes.