Skip to main content

Research Repository

Advanced Search

Semiclassical Green's functions and an instanton formulation of electron-transfer rates in the nonadiabatic limit

Richardson, Jeremy O.; Bauer, Rainer; Thoss, Michael

Semiclassical Green's functions and an instanton formulation of electron-transfer rates in the nonadiabatic limit Thumbnail


Authors

Jeremy O. Richardson

Rainer Bauer

Michael Thoss



Abstract

We present semiclassical approximations to Green’s functions of multidimensional systems, extending Gutzwiller’s work to the classically forbidden region. Based on steepest-descent integrals over these functions, we derive an instanton method for computing the rate of nonadiabatic reactions, such as electron transfer, in the weak-coupling limit, where Fermi’s golden-rule can be employed. This generalizes Marcus theory to systems for which the environment free-energy curves are not harmonic and where nuclear tunnelling plays a role. The derivation avoids using the Im F method or short-time approximations to real-time correlation functions. A clear physical interpretation of the nuclear tunnelling processes involved in an electron-transfer reaction is thus provided. In Paper II [J. O. Richardson, J. Chem. Phys. 143, 134116 (2015)], we discuss numerical evaluation of the formulae.

Citation

Richardson, J. O., Bauer, R., & Thoss, M. (2015). Semiclassical Green's functions and an instanton formulation of electron-transfer rates in the nonadiabatic limit. The Journal of Chemical Physics, 143(13), Article 134115. https://doi.org/10.1063/1.4932361

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 134115
DOI https://doi.org/10.1063/1.4932361

Files

Published Journal Article (824 Kb)
PDF

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., Bauer, Rainer & Thoss, Michael (2015). Semiclassical Green's functions and an instanton formulation of electron-transfer rates in the nonadiabatic limit. The Journal of Chemical Physics 143(13): 134115 and may be found at https://doi.org/10.1063/1.4932361




You might also like



Downloadable Citations