Issue 34, 2023

The Marcus dimension: identifying the nuclear coordinate for electron transfer from ab initio calculations

Abstract

The Marcus model forms the foundation for all modern discussion of electron transfer (ET). In this model, ET results in a change in diabatic potential energy surfaces, separated along an ET nuclear coordinate. This coordinate accounts for all nuclear motion that promotes electron transfer. It is usually assumed to be dominated by a collective asymmetric vibrational motion of the redox sites involved in the ET. However, this coordinate is rarely quantitatively specified. Instead, it remains a nebulous concept, rather than a tool for gaining true insight into the ET pathway. Herein, we describe an ab initio approach for quantifying the ET coordinate and demonstrate it for a series of dinitroradical anions. Using sampling methods at finite temperature combined with density functional theory calculations, we find that the electron transfer can be followed using the energy separation between potential energy surfaces and the extent of electron localization. The precise nuclear motion that leads to electron transfer is then obtained as a linear combination of normal modes. Once the coordinate is identified, we find that evolution along it results in a change in diabatic state and optical excitation energy, as predicted by the Marcus model. Thus, we conclude that a single dimension of the electron transfer described in Marcus–Hush theory can be described as a well-defined nuclear motion. Importantly, our approach allows the separation of the intrinsic electron transfer coordinate from other structural relaxations and environmental influences. Furthermore, the barrier separating the adiabatic minima was found to be sufficiently thin to enable heavy-atom tunneling in the ET process.

Graphical abstract: The Marcus dimension: identifying the nuclear coordinate for electron transfer from ab initio calculations

Supplementary files

Article information

Article type
Edge Article
Submitted
16 mar 2023
Accepted
06 avq 2023
First published
08 avq 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2023,14, 9213-9225

The Marcus dimension: identifying the nuclear coordinate for electron transfer from ab initio calculations

A. Šrut, B. J. Lear and V. Krewald, Chem. Sci., 2023, 14, 9213 DOI: 10.1039/D3SC01402A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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