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

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.
Authors:
; ;  [1]
  1. Institut für Theoretische Physik und Interdisziplinäres Zentrum für Molekulare Materialien, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Staudtstraße 7/B2, 91058 Erlangen (Germany)
Publication Date:
OSTI Identifier:
22489673
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 143; Journal Issue: 13; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DIAGRAMS; ELECTRON TRANSFER; EVALUATION; FREE ENERGY; INTEGRALS; SEMICLASSICAL APPROXIMATION; TUNNEL EFFECT