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Title: Simulating conical intersection dynamics in the condensed phase with hybrid quantum master equations

Abstract

We introduce a framework for simulating relaxation dynamics through a conical intersection of an open quantum system that combines methods to approximate the motion of degrees of freedom with disparate time and energy scales. In the vicinity of a conical intersection, a few degrees of freedom render the nuclear dynamics nonadiabatic with respect to the electronic degrees of freedom. We treat these strongly coupled modes by evolving their wavepacket dynamics in the absence of additional coupling exactly. The remaining weakly coupled nuclear degrees of freedom are partitioned into modes that are fast relative to the nonadiabatic coupling and those that are slow. The fast degrees of freedom can be traced out and treated with second-order perturbation theory in the form of the time-convolutionless master equation. The slow degrees of freedom are assumed to be frozen over the ultrafast relaxation and treated as sources of static disorder. Similarly, we adopt the recently developed frozen-mode extension to second-order quantum master equations. We benchmark this approach to numerically exact results in models of pyrazine internal conversion and rhodopsin photoisomerization. We use this framework to study the dependence of the quantum yield on the reorganization energy and the characteristic time scale of the bathmore » in a two-mode model of photoisomerization. We believe that the yield is monotonically increasing with reorganization energy for a Markovian bath but monotonically decreasing with reorganization energy for a non-Markovian bath. This reflects the subtle interplay between dissipation and decoherence in conical intersection dynamics in the condensed phase.« less

Authors:
 [1]; ORCiD logo [1]
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  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR). Scientific Discovery through Advanced Computing (SciDAC)
OSTI Identifier:
1577599
Alternate Identifier(s):
OSTI ID: 1530912
Grant/Contract Number:  
AC02-05CH11231; AC02- 05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 1; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Schile, Addison J., and Limmer, David T. Simulating conical intersection dynamics in the condensed phase with hybrid quantum master equations. United States: N. p., 2019. Web. doi:10.1063/1.5106379.
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Schile, Addison J., & Limmer, David T. Simulating conical intersection dynamics in the condensed phase with hybrid quantum master equations. United States. https://doi.org/10.1063/1.5106379
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Schile, Addison J., and Limmer, David T. Wed . "Simulating conical intersection dynamics in the condensed phase with hybrid quantum master equations". United States. https://doi.org/10.1063/1.5106379. https://www.osti.gov/servlets/purl/1577599.
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@article{osti_1577599,
title = {Simulating conical intersection dynamics in the condensed phase with hybrid quantum master equations},
author = {Schile, Addison J. and Limmer, David T.},
abstractNote = {We introduce a framework for simulating relaxation dynamics through a conical intersection of an open quantum system that combines methods to approximate the motion of degrees of freedom with disparate time and energy scales. In the vicinity of a conical intersection, a few degrees of freedom render the nuclear dynamics nonadiabatic with respect to the electronic degrees of freedom. We treat these strongly coupled modes by evolving their wavepacket dynamics in the absence of additional coupling exactly. The remaining weakly coupled nuclear degrees of freedom are partitioned into modes that are fast relative to the nonadiabatic coupling and those that are slow. The fast degrees of freedom can be traced out and treated with second-order perturbation theory in the form of the time-convolutionless master equation. The slow degrees of freedom are assumed to be frozen over the ultrafast relaxation and treated as sources of static disorder. Similarly, we adopt the recently developed frozen-mode extension to second-order quantum master equations. We benchmark this approach to numerically exact results in models of pyrazine internal conversion and rhodopsin photoisomerization. We use this framework to study the dependence of the quantum yield on the reorganization energy and the characteristic time scale of the bath in a two-mode model of photoisomerization. We believe that the yield is monotonically increasing with reorganization energy for a Markovian bath but monotonically decreasing with reorganization energy for a non-Markovian bath. This reflects the subtle interplay between dissipation and decoherence in conical intersection dynamics in the condensed phase.},
doi = {10.1063/1.5106379},
journal = {Journal of Chemical Physics},
number = 1,
volume = 151,
place = {United States},
year = {Wed Jul 03 00:00:00 EDT 2019},
month = {Wed Jul 03 00:00:00 EDT 2019}
}
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https://doi.org/10.1063/1.5106379
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Cited by: 16 works
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Figures / Tables:

FIG. 1 FIG. 1: Diabatic populations given by Eq. (37) for a bath with ωc = 0.0132 eV with values of the reorganization energy Er = 0.006 571 eV (a) and Er = 0.013 14 eV (b). Shown in the inset of (a) are the potential energies for each electronic state alongmore » the coordinate qt . In the inset of (b), shown are the results for secular Redfield theory with frozen modes. HEOM data were taken from Ref. 51.« less
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    Works referencing / citing this record:

    Special topic on dynamics of open quantum systems
    journal, January 2020

    • Berkelbach, Timothy C.; Thoss, Michael
    • The Journal of Chemical Physics, Vol. 152, Issue 2
    • DOI: 10.1063/1.5142731

    Quantum dissipative systems beyond the standard harmonic model: Features of linear absorption and dynamics
    journal, October 2019

    • Smith, Luke D.; Dijkstra, Arend G.
    • The Journal of Chemical Physics, Vol. 151, Issue 16
    • DOI: 10.1063/1.5122896

    Statistical distributions of the tuning and coupling collective modes at a conical intersection using the hierarchical equations of motion
    journal, December 2019

    • Mangaud, Etienne; Lasorne, Benjamin; Atabek, Osman
    • The Journal of Chemical Physics, Vol. 151, Issue 24
    • DOI: 10.1063/1.5128852
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