Ring-polymer instanton theory of electron transfer in the nonadiabatic limit

Richardson, Jeremy O.

Abstract

We take the golden-rule instanton method derived in the previous paper [J. O. Richardson, R. Bauer, and M. Thoss, J. Chem. Phys. 143, 134115 (2015)] and reformulate it using a ring-polymer instanton approach. This gives equations which can be used to compute the rates of electron-transfer reactions in the nonadiabatic (golden-rule) limit numerically within a semiclassical approximation. The multidimensional ring-polymer instanton trajectories are obtained efficiently by minimization of the action. In this form, comparison with Wolynes’ quantum instanton method [P. G. Wolynes, J. Chem. Phys. 87, 6559 (1987)] is possible and we show that our semiclassical approach is the steepest-descent limit of this method. We discuss advantages and disadvantages of both methods and give examples of where the new approach is more accurate.

Citation

Richardson, J. O. (2015). Ring-polymer instanton theory of electron transfer in the nonadiabatic limit. The Journal of Chemical Physics, 143(13), Article 134116. https://doi.org/10.1063/1.4932362

• Journal Article Type: Article
• Acceptance Date: Sep 23, 2015
• Online Publication Date: Oct 7, 2015
• Publication Date: Oct 7, 2015
• Deposit Date: Feb 7, 2016
• Publicly Available Date: Jun 26, 2018
• Journal: Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 143
• Issue: 13
• Article Number: 134116
• DOI: https://doi.org/10.1063/1.4932362
• Public URL: https://durham-repository.worktribe.com/output/1389600