Nonadiabatic ring-polymer instanton rate theory: a generalised dividing-surface approach

• URL: http://arxiv.org/abs/2505.04770v1
• Date: Wed, 07 May 2025 19:47:59 GMT
• Title: Nonadiabatic ring-polymer instanton rate theory: a generalised dividing-surface approach
• Authors: Rhiannon A. Zarotiadis, Joseph E. Lawrence, Jeremy O. Richardson,
• Abstract summary: Ring-polymer instanton theories offer a promising approach to solve this problem.<n>We develop a generalised nonadiabatic instanton rate theory that bridges between two limits.<n>The resulting theory approximates the quantum-mechanically exact rates well for the systems studied.
• Score: 0.0
• License: http://creativecommons.org/licenses/by/4.0/
• Abstract: Constructing an accurate approximation to nonadiabatic rate theory which is valid for arbitrary values of the electronic coupling has been a long-standing challenge in theoretical chemistry. Ring-polymer instanton theories offer a very promising approach to solve this problem, since they can be rigorously derived using semiclassical approximations and can capture nuclear quantum effects such as tunnelling and zero-point energy at a cost similar to that of a classical calculation. A successful instanton rate theory already exists within the Born--Oppenheimer approximation, for which the optimal tunnelling pathway is located on a single adiabatic surface. A related instanton theory has also been developed for nonadiabatic reactions using two weakly-coupled diabatic surfaces within the framework of Fermi's golden rule. However, many chemical reactions do not satisfy the conditions of either limit. By employing a tunable dividing surface which measures the flux both along nuclear coordinates as well as between electronic states, we develop a generalised nonadiabatic instanton rate theory that bridges between these two limits. The resulting theory approximates the quantum-mechanically exact rates well for the systems studied and, in addition, offers a novel mechanistic perspective on nonadiabatic reactions.

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