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

Huo, Pengfei and Miller, Thomas F., III and Coker, David F. (2013) Communication: Predictive partial linearized path integral simulation of condensed phase electron transfer dynamics. Journal of Chemical Physics, 139 (15). Art. No. 151103. ISSN 0021-9606. doi:10.1063/1.4826163. https://resolver.caltech.edu/CaltechAUTHORS:20131121-153219343

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Abstract

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.4826163DOIArticle
ORCID:
AuthorORCID
Huo, Pengfei0000-0002-8639-9299
Miller, Thomas F., III0000-0002-1882-5380
Additional Information:© 2013 American Institute of Physics Publishing LLC. Received 19 August 2013; accepted 6 October 2013; published online 17 October 2013. We acknowledge NSF and DOE support (CHE-0911635 and DE-SC0006598). P.H. thanks J. Straub, N. Ananth, and D. Reichman for valuable discussions.
Funders:
Funding AgencyGrant Number
NSFCHE-0911635
Department of Energy (DOE)DE-SC0006598
Issue or Number:15
DOI:10.1063/1.4826163
Record Number:CaltechAUTHORS:20131121-153219343
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20131121-153219343
Official Citation: Communication: Predictive partial linearized path integral simulation of condensed phase electron transfer dynamics Pengfei Huo , Thomas F. Miller III and David F. Coker J. Chem. Phys. 139, 151103 (2013); http://dx.doi.org/10.1063/1.4826163
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:42634
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:21 Nov 2013 23:49
Last Modified:10 Nov 2021 16:26

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