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Title: Communication: Predictive partial linearized path integral simulation of condensed phase electron transfer dynamics

A partial linearized path integral approach is used to calculate the condensed phase electron transfer (ET) rate by directly evaluating the flux-flux/flux-side quantum time correlation functions. We demonstrate for a simple ET model that this approach can reliably capture the transition between non-adiabatic and adiabatic regimes as the electronic coupling is varied, while other commonly used semi-classical methods are less accurate over the broad range of electronic couplings considered. Further, we show that the approach reliably recovers the Marcus turnover as a function of thermodynamic driving force, giving highly accurate rates over four orders of magnitude from the normal to the inverted regimes. We also demonstrate that the approach yields accurate rate estimates over five orders of magnitude of inverse temperature. Finally, the approach outlined here accurately captures the electronic coherence in the flux-flux correlation function that is responsible for the decreased rate in the inverted regime.
Authors:
;  [1] ;  [2]
  1. Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125 (United States)
  2. Department of Chemistry, Boston University, 590 Commonwealth Avenue, Boston, Massachusetts 02215 (United States)
Publication Date:
OSTI Identifier:
22220398
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 139; Journal Issue: 15; Other Information: (c) 2013 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; CHARGE EXCHANGE; CORRELATION FUNCTIONS; ELECTRON TRANSFER; PATH INTEGRALS; REACTION KINETICS; SIMULATION