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Title: Numerical tests of coherence-corrected surface hopping methods using a donor-bridge-acceptor model system

Abstract

Surface hopping (SH) is a popular mixed quantum-classical method for modeling nonadiabatic excited state processes in molecules and condensed phase materials. The method is simple, efficient, and easy to implement, but the use of classical and independent nuclear trajectories introduces an overcoherence in the electronic density matrix which, if ignored, often leads to spurious results, such as overestimated reaction rates. Several methods have been proposed to incorporate decoherence into SH simulations, but a lack of insightful benchmarks makes their relative accuracy unknown. Herein, we run numerical simulations of common coherence-corrected SH methods including Truhlar’s decay-of-mixing (DOM) and Subotnik’s augmented SH using a Donor-bridge-Acceptor (DbA) model system. Numerical simulations are carried out in the superexchange regime, where charge transfer proceeds from a donor to an acceptor as a result of donor-bridge and bridge-acceptor couplings. The computed donor-to-acceptor reaction rates are compared to the reference Marcus theory results. For the DbA model under consideration, augmented SH recovers Marcus theory with quantitative accuracy, whereas DOM is only qualitatively accurate depending on whether predefined parameters in the decoherence rate are chosen wisely. We propose a general method for parameterizing the decoherence rate in the DOM method, which improves the method’s reaction rates and presumablymore » increases its transferability. Altogether, the decoherence method of choice must be chosen with great care and this work provides insight using an exactly solvable model.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]
+ Show Author Affiliations
  1. Univ. of Southern California, Los Angeles, CA (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Zhejiang Univ., Hangzhou (China)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Skolkovo Institute of Science and Technology, Moscow (Russia)
  4. Univ. of Southern California, Los Angeles, CA (United States)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1532718
Report Number(s):
LA-UR-19-20761
Journal ID: ISSN 0021-9606
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 19; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 36 MATERIALS SCIENCE; Material Science

Citation Formats

Sifain, Andrew E., Wang, Linjun, Tretiak, Sergei, and Prezhdo, Oleg V. Numerical tests of coherence-corrected surface hopping methods using a donor-bridge-acceptor model system. United States: N. p., 2019. Web. doi:10.1063/1.5092999.
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Sifain, Andrew E., Wang, Linjun, Tretiak, Sergei, & Prezhdo, Oleg V. Numerical tests of coherence-corrected surface hopping methods using a donor-bridge-acceptor model system. United States. https://doi.org/10.1063/1.5092999
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Sifain, Andrew E., Wang, Linjun, Tretiak, Sergei, and Prezhdo, Oleg V. Thu . "Numerical tests of coherence-corrected surface hopping methods using a donor-bridge-acceptor model system". United States. https://doi.org/10.1063/1.5092999. https://www.osti.gov/servlets/purl/1532718.
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@article{osti_1532718,
title = {Numerical tests of coherence-corrected surface hopping methods using a donor-bridge-acceptor model system},
author = {Sifain, Andrew E. and Wang, Linjun and Tretiak, Sergei and Prezhdo, Oleg V.},
abstractNote = {Surface hopping (SH) is a popular mixed quantum-classical method for modeling nonadiabatic excited state processes in molecules and condensed phase materials. The method is simple, efficient, and easy to implement, but the use of classical and independent nuclear trajectories introduces an overcoherence in the electronic density matrix which, if ignored, often leads to spurious results, such as overestimated reaction rates. Several methods have been proposed to incorporate decoherence into SH simulations, but a lack of insightful benchmarks makes their relative accuracy unknown. Herein, we run numerical simulations of common coherence-corrected SH methods including Truhlar’s decay-of-mixing (DOM) and Subotnik’s augmented SH using a Donor-bridge-Acceptor (DbA) model system. Numerical simulations are carried out in the superexchange regime, where charge transfer proceeds from a donor to an acceptor as a result of donor-bridge and bridge-acceptor couplings. The computed donor-to-acceptor reaction rates are compared to the reference Marcus theory results. For the DbA model under consideration, augmented SH recovers Marcus theory with quantitative accuracy, whereas DOM is only qualitatively accurate depending on whether predefined parameters in the decoherence rate are chosen wisely. We propose a general method for parameterizing the decoherence rate in the DOM method, which improves the method’s reaction rates and presumably increases its transferability. Altogether, the decoherence method of choice must be chosen with great care and this work provides insight using an exactly solvable model.},
doi = {10.1063/1.5092999},
journal = {Journal of Chemical Physics},
number = 19,
volume = 150,
place = {United States},
year = {2019},
month = {5}
}
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