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Direct simulation of electron transfer using ring polymer molecular dynamics: Comparison with semiclassical instanton theory and exact quantum methods

Menzeleev, Artur R. and Ananth, Nandini and Miller, Thomas F., III (2011) Direct simulation of electron transfer using ring polymer molecular dynamics: Comparison with semiclassical instanton theory and exact quantum methods. Journal of Chemical Physics, 135 (7). Art. No. 074106. ISSN 0021-9606.

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The use of ring polymer molecular dynamics (RPMD) for the direct simulation of electron transfer (ET) reaction dynamics is analyzed in the context of Marcus theory, semiclassical instanton theory, and exact quantum dynamics approaches. For both fully atomistic and system-bath representations of condensed-phase ET, we demonstrate that RPMD accurately predicts both ET reaction rates and mechanisms throughout the normal and activationless regimes of the thermodynamic driving force. Analysis of the ensemble of reactive RPMD trajectories reveals the solvent reorganization mechanism for ET that is anticipated in the Marcus rate theory, and the accuracy of the RPMD rate calculation is understood in terms of its exact description of statistical fluctuations and its formal connection to semiclassical instanton theory for deep-tunneling processes. In the inverted regime of the thermodynamic driving force, neither RPMD nor a related formulation of semiclassical instanton theory capture the characteristic turnover in the reaction rate; comparison with exact quantum dynamics simulations reveals that these methods provide inadequate quantization of the real-time electronic-state dynamics in the inverted regime.

Item Type:Article
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Miller, Thomas F., III0000-0002-1882-5380
Additional Information:© 2011 American Institute of Physics. Received 11 July 2011; accepted 25 July 2011; published online 17 August 2011. This work was supported by the U.S. Office of Naval Research (USONR) under Grant No. N00014-10-1-0884 and National Science Foundation (NSF) CAREER Award under Grant No. CHE-1057112. Computing resources were provided by the National Energy Research Scientific Computing Center (NERSC) and the Oak Ridge Leadership Computing Facility (OLCF). T.F.M. acknowledges support from a Camille and Henry Dreyfus Foundation New Faculty Award and an Alfred P. Sloan Foundation Research Fellowship.
Funding AgencyGrant Number
Office of Naval Research (ONR)N00014-10-1-0884
Camille and Henry Dreyfus FoundationUNSPECIFIED
Alfred P. Sloan FoundationUNSPECIFIED
Subject Keywords:charge exchange; molecular dynamics method; quantum theory; reaction kinetics theory; reaction rate constants; tunnelling
Issue or Number:7
Classification Code:PACS: 82.30.Fi, 82.20.Xr, 82.20.Wt, 82.20.Pm, 82.20.Hf, 82.20.Fd
Record Number:CaltechAUTHORS:20110909-122016964
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:25276
Deposited By: Jason Perez
Deposited On:09 Sep 2011 20:12
Last Modified:03 Oct 2019 03:04

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