Jeremy O. Richardson
Semiclassical Green's functions and an instanton formulation of electron-transfer rates in the nonadiabatic limit
Richardson, Jeremy O.; Bauer, Rainer; Thoss, Michael
Authors
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 |
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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., 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
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