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

• Published in: The Journal of chemical physics 2013-10, Vol.139 (15), p.151103-151103
• Main Authors: Huo, Pengfei, Miller, 3rd, Thomas F, Coker, David F
• Format: Article
• Language: English
• Subjects: CHARGE EXCHANGE; CORRELATION FUNCTIONS; ELECTRON TRANSFER; Electron Transport; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; PATH INTEGRALS; Quantum Theory; REACTION KINETICS; SIMULATION; Thermodynamics; Time Factors
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.4826163

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.