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Title: A symmetrical quasi-classical windowing model for the molecular dynamics treatment of non-adiabatic processes involving many electronic states

Abstract

In the previous work of Cotton and Miller [J. Chem. Phys. 145, 144108 (2016)], an improved symmetrical quasi-classical (SQC) windowing model for the molecular dynamics treatment of electronically non-adiabatic processes was developed in order to extend the original SQC approach to the regime of weak-coupling between the electronic states. Furthermore, the improved SQC model—based on triangular-shaped window functions—handled the weak-coupling limit as intended and, as a bonus, was shown to be universally superior to the original square/histogram SQC windowing model over all coupling regimes, but only for treating systems of two electronic states, as no higher-dimensional generalization was evident. This paper, therefore, provides a generalized version for treating an arbitrary number of electronic states. By construction, the benefits of the two-state triangle model—seamless treatment of weak-coupling and improved accuracy in all coupling regimes—carry over to the generalized version. Far more significant, however, is that the new model provides vastly improved windowing statistics in higher dimensions, enabling the SQC simulation of electronically non-adiabatic processes involving many more relevant electronic states than was previously practical. Capabilities are demonstrated with respect to a 24 pigment trimer model of the Fenna-Matthews-Olson light-harvesting complex, as well as treating similar 48- and 96-electronic state model problems,more » illustrating the scaling properties of the new method.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]
  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)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1530414
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 10; 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; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Cotton, Stephen J., and Miller, William H. A symmetrical quasi-classical windowing model for the molecular dynamics treatment of non-adiabatic processes involving many electronic states. United States: N. p., 2019. Web. doi:10.1063/1.5087160.
Cotton, Stephen J., & Miller, William H. A symmetrical quasi-classical windowing model for the molecular dynamics treatment of non-adiabatic processes involving many electronic states. United States. doi:10.1063/1.5087160.
Cotton, Stephen J., and Miller, William H. Mon . "A symmetrical quasi-classical windowing model for the molecular dynamics treatment of non-adiabatic processes involving many electronic states". United States. doi:10.1063/1.5087160. https://www.osti.gov/servlets/purl/1530414.
@article{osti_1530414,
title = {A symmetrical quasi-classical windowing model for the molecular dynamics treatment of non-adiabatic processes involving many electronic states},
author = {Cotton, Stephen J. and Miller, William H.},
abstractNote = {In the previous work of Cotton and Miller [J. Chem. Phys. 145, 144108 (2016)], an improved symmetrical quasi-classical (SQC) windowing model for the molecular dynamics treatment of electronically non-adiabatic processes was developed in order to extend the original SQC approach to the regime of weak-coupling between the electronic states. Furthermore, the improved SQC model—based on triangular-shaped window functions—handled the weak-coupling limit as intended and, as a bonus, was shown to be universally superior to the original square/histogram SQC windowing model over all coupling regimes, but only for treating systems of two electronic states, as no higher-dimensional generalization was evident. This paper, therefore, provides a generalized version for treating an arbitrary number of electronic states. By construction, the benefits of the two-state triangle model—seamless treatment of weak-coupling and improved accuracy in all coupling regimes—carry over to the generalized version. Far more significant, however, is that the new model provides vastly improved windowing statistics in higher dimensions, enabling the SQC simulation of electronically non-adiabatic processes involving many more relevant electronic states than was previously practical. Capabilities are demonstrated with respect to a 24 pigment trimer model of the Fenna-Matthews-Olson light-harvesting complex, as well as treating similar 48- and 96-electronic state model problems, illustrating the scaling properties of the new method.},
doi = {10.1063/1.5087160},
journal = {Journal of Chemical Physics},
number = 10,
volume = 150,
place = {United States},
year = {2019},
month = {3}
}

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    Works referencing / citing this record:

    Combining Meyer–Miller Hamiltonian with electronic structure methods for on-the-fly nonadiabatic dynamics simulations: implementation and application
    journal, January 2019

    • Tang, Diandong; Fang, Wei-Hai; Shen, Lin
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 31
    • DOI: 10.1039/c9cp02682g

    Combining Meyer–Miller Hamiltonian with electronic structure methods for on-the-fly nonadiabatic dynamics simulations: implementation and application
    journal, January 2019

    • Tang, Diandong; Fang, Wei-Hai; Shen, Lin
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 31
    • DOI: 10.1039/c9cp02682g