Electronic origin of reorganization energy in interfacial electron transfer

TL;DR

This paper demonstrates that the electrode's electronic density of states significantly influences reorganization energy and electron transfer rates at interfaces, challenging traditional views that only electrolyte factors matter.

Contribution

It reveals the electrode DOS's central role in reorganization energy, using atomically layered heterostructures to modulate and measure ET kinetics.

Findings

Electrode DOS strongly modulates reorganization energy.

Variation in ET rate linked to image potential localization.

Redefines understanding of interfacial electron transfer mechanisms.

Abstract

Electron transfer (ET) reactions underpin energy conversion and chemical transformations in both biological and abiological systems. The efficiency of any ET process relies on achieving a desired ET rate within an optimal driving force range. Marcus theory provides a microscopic framework for understanding the activation free energy, and thus the rate, of ET in terms of a key parameter: the reorganization energy. For electrified solid-liquid interfaces, it has long been conventionally understood that only factors in the electrolyte phase are responsible for determining the reorganization energy and the electronic density of states (DOS) of the electrode serves only to dictate the number of thermally accessible channels for ET. Here we show instead that the electrode DOS plays a central role in governing the reorganization energy, far outweighing its conventionally assumed role. Using atomically layered heterostructures, we tune the DOS of graphene and measure outer-sphere ET kinetics. We find the ensuing variation in ET rate arises from strong modulation in a reorganization energy associated with image potential localization in the electrode. This work redefines the traditional paradigm of heterogeneous ET kinetics, revealing a deeper role of the electrode electronic structure in interfacial reactivity.