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This study extends Marcus theory to coupled ion-electron transfer by incorporating interfacial anisotropy, enabling direct calculation of free-energy surfaces from first-principles trajectories. The authors demonstrate that two-dimensional saddle-point barriers for reactions like CO2 redox differ significantly from traditional one-dimensional models, offering a more accurate microscopic framework for electrochemical kinetics. This advancement provides a rigorous computational route to predict current-overpotential relations without relying on simplified coordinate assumptions.
Ab Initio Free Energy Surfaces for Coupled Ion-Electron Transfer
arXiv:2510.19106v5 Announce Type: replace-cross Abstract: Although coupled ion-electron transfer (CIET) has emerged as a powerful framework to rationalize the kinetics of Faradaic reactions, its mechanism has lacked a fully microscopic, first-principles description. Here we show that the coupling of electron-transfer to ion-transfer can be understood as an extension of Marcus theory in which the ensemble of diabatic nuclear configurations is conditioned on a classical collective variable describing the interfacial anisotropy. This formalism enables direct construction of the CIET free-energy surface from constrained ab initio trajectories, providing a first-principles route to electrochemical current-overpotential relations. We demonstrate this method for CO2 redox on a gold electrode and find that the resulting two-dimensional saddle-point barriers differ substantially from one-dimensional treatments that consider only electron- or ion-transfer coordinates individually.
Abstract:Although coupled ion-electron transfer (CIET) has emerged as a powerful framework to rationalize the kinetics of Faradaic reactions, its mechanism has lacked a fully microscopic, first-principles description. Here we show that the coupling of electron-transfer to ion-transfer can be understood as an extension of Marcus theory in which the ensemble of diabatic nuclear configurations is conditioned on a classical collective variable describing the interfacial anisotropy. This formalism enables direct construction of the CIET free-energy surface from constrained ab initio trajectories, providing a first-principles route to electrochemical current-overpotential relations. We demonstrate this method for CO2 redox on a gold electrode and find that the resulting two-dimensional saddle-point barriers differ substantially from one-dimensional treatments that consider only electron- or ion-transfer coordinates individually.
Chemical Physics (physics.chem-ph); Materials Science (cond-mat.mtrl-sci); Quantum Physics (quant-ph)
arXiv:2510.19106 [physics.chem-ph]
(or arXiv:2510.19106v5 [physics.chem-ph] for this version)
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