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Direct simulation of proton-coupled electron transfer across multiple regimes

Kretchmer, Joshua S. and Miller, Thomas F., III (2013) Direct simulation of proton-coupled electron transfer across multiple regimes. Journal of Chemical Physics, 138 (13). Art. No. 134109. ISSN 0021-9606. doi:10.1063/1.4797462.

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The coupled transfer of electrons and protons is a central feature of biological and molecular catalysis, yet fundamental aspects of these reactions remain poorly understood. In this study, we extend the ring polymer molecular dynamics (RPMD) method to enable direct simulation of proton-coupled electron transfer (PCET) reactions across a wide range of physically relevant regimes. In a system-bath model for symmetric, co-linear PCET in the condensed phase, RPMD trajectories reveal distinct kinetic pathways associated with sequential and concerted PCET reaction mechanisms, and it is demonstrated that concerted PCET proceeds by a solvent-gating mechanism in which the reorganization energy is mitigated by charge cancellation among the transferring particles. We further employ RPMD to study the kinetics and mechanistic features of concerted PCET reactions across multiple coupling regimes, including the fully non-adiabatic (both electronically and vibrationally non-adiabatic), partially adiabatic (electronically adiabatic, but vibrationally non-adiabatic), and fully adiabatic (both electronically and vibrationally adiabatic) limits. Comparison of RPMD with the results of PCET rate theories demonstrates the applicability of the direct simulation method over a broad range of conditions; it is particularly notable that RPMD accurately predicts the crossover in the thermal reaction rates between different coupling regimes while avoiding a priori assumptions about the PCET reaction mechanism. Finally, by utilizing the connections between RPMD rate theory and semiclassical instanton theory, we show that analysis of ring-polymer configurations in the RPMD transition path ensemble enables the a posteriori determination of the coupling regime for the PCET reaction. This analysis reveals an intriguing and distinct “transient-proton-bridge” mechanism for concerted PCET that emerges in the transition between the proton-mediated electron superexchange mechanism for fully non-adiabatic PCET and the hydrogen atom transfer mechanism for partially adiabatic PCET. Taken together, these results provide a unifying picture of the mechanisms and physical driving forces that govern PCET across a wide range of physical regimes, and they raise the possibility for PCET mechanisms that have not been previously reported.

Item Type:Article
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URLURL TypeDescription
Kretchmer, Joshua S.0000-0003-3468-0481
Miller, Thomas F., III0000-0002-1882-5380
Additional Information:© 2013 American Institute of Physics. Received 18 January 2013; accepted 10 March 2013; published online 2 April 2013. This work was supported by the National Science Foundation (NSF) CAREER Award under Grant No. CHE-1057112 and the (U.S.) Department of Energy (DOE) under Grant No. DE-SC0006598. Additionally, J.S.K. acknowledges support from a NSF Graduate Research Fellowship under Grant No. DGE-1144469, and T.F.M. acknowledges support from a Camille and Henry Dreyfus Foundation New Faculty Award and an Alfred P. Sloan Foundation Research Fellowship. Computing resources were provided by the National Energy Research Scientific Computing Center (NERSC) (DE-AC02-05CH11231) and the Oak Ridge Leadership Computing Facility (OLCF) (DE-AC05-00OR22725). The authors sincerely thank Artur Menzeleev and Nandini Ananth for helpful conversations.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0006598
NSF Graduate Research FellowshipDGE-1144469
Camille and Henry Dreyfus Foundation New Faculty AwardUNSPECIFIED
Alfred P. Sloan Foundation Research FellowshipUNSPECIFIED
National Energy Research Scientific Computing Center (NERSC)DE-AC02-05CH11231
Oak Ridge Leadership Computing Facility (OLCF)DE-AC05-00OR22725
Subject Keywords:charge exchange; chemical exchanges; heat of reaction; molecular dynamics method; polymers; reaction kinetics theory
Issue or Number:13
Classification Code:PACS: 82.35.-x; 82.20.Gk; 82.20.Ln; 82.20.Fd; 82.30.Fi; 82.30.Hk
Record Number:CaltechAUTHORS:20130603-112629415
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Official Citation:Direct simulation of proton-coupled electron transfer across multiple regimes Joshua S. Kretchmer Thomas F. Miller and III, J. Chem. Phys. 138, 134109 (2013), DOI:10.1063/1.4797462
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:38758
Deposited By: Jason Perez
Deposited On:05 Jun 2013 23:13
Last Modified:09 Nov 2021 23:39

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