Ab Initio Free Energy Surfaces for Coupled Ion-Electron Transfer

• URL: http://arxiv.org/abs/2510.19106v3
• Date: Tue, 04 Nov 2025 17:34:15 GMT
• Title: Ab Initio Free Energy Surfaces for Coupled Ion-Electron Transfer
• Authors: Ethan Abraham, Martin Z. Bazant, Troy Van Voorhis,
• Abstract summary: Theory of electron transfer assumes that diabatic energy gaps are sampled from a single ensemble.<n>We develop a formalism that enables calculation of the resulting Coupled Ion-Electron Transfer (CIET) free-energy surface directly from constrained ab initio trajectories.
• Score: 0.0
• License: http://creativecommons.org/licenses/by/4.0/
• Abstract: The Marcus theory of electron transfer assumes that diabatic energy gaps are sampled from a single ensemble. This assumption can break down in spatially anisotropic environments, such as Faradaic reactions at electrochemical interfaces, where distinct solvent ensembles arise along a collective variable describing the anisotropy. Treating this collective variable as an additional reaction coordinate linearly independent from the Marcus reaction coordinate, we develop a formalism that enables calculation of the resulting Coupled Ion-Electron Transfer (CIET) free-energy surface directly from constrained ab initio trajectories. Applied to CO2 redox on a gold electrode, this method reveals strong coupling to the anisotropy, predicting significantly different activation barriers compared to either coordinate alone.

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