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

Richardson, Jeremy O.

doi:10.1063/1.4932362

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

Richardson, Jeremy O.

Authors

Jeremy O. Richardson

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

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Copyright Statement
© 2015 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in Richardson, Jeremy O. (2015). Ring-polymer instanton theory of electron transfer in the nonadiabatic limit. The Journal of Chemical Physics 143(13): 134116 and may be found at https://doi.org/10.1063/1.4932362