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Title: Path integral molecular dynamics for exact quantum statistics of multi-electronic-state systems

Abstract

An exact approach to compute physical properties for general multi-electronic-state (MES) systems in thermal equilibrium is presented. The approach is extended from our recent progress on path integral molecular dynamics (PIMD), for quantum statistical mechanics when a single potential energy surface is involved. We first define an effective potential function that is numerically favorable for MES-PIMD and then derive corresponding estimators in MES-PIMD for evaluating various physical properties. Furthermore, its application to several representative one-dimensional and multi-dimensional models demonstrates that MES-PIMD in principle offers a practical tool in either of the diabatic and adiabatic representations for studying exact quantum statistics of complex/large MES systems when the Born-Oppenheimer approximation, Condon approximation, and harmonic bath approximation are broken.

Authors:
 [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Peking Univ., Beijing (China). Beijing National Laboratory for Molecular Sciences, Institute of Theoretical and Computational Chemistry, College of Chemistry and Molecular Engineering
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)
OSTI Identifier:
1498058
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; 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

Liu, Xinzijian, and Liu, Jian. Path integral molecular dynamics for exact quantum statistics of multi-electronic-state systems. United States: N. p., 2017. Web. doi:10.1063/1.5005059.
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Liu, Xinzijian, & Liu, Jian. Path integral molecular dynamics for exact quantum statistics of multi-electronic-state systems. United States. https://doi.org/10.1063/1.5005059
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Liu, Xinzijian, and Liu, Jian. Mon . "Path integral molecular dynamics for exact quantum statistics of multi-electronic-state systems". United States. https://doi.org/10.1063/1.5005059. https://www.osti.gov/servlets/purl/1498058.
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@article{osti_1498058,
title = {Path integral molecular dynamics for exact quantum statistics of multi-electronic-state systems},
author = {Liu, Xinzijian and Liu, Jian},
abstractNote = {An exact approach to compute physical properties for general multi-electronic-state (MES) systems in thermal equilibrium is presented. The approach is extended from our recent progress on path integral molecular dynamics (PIMD), for quantum statistical mechanics when a single potential energy surface is involved. We first define an effective potential function that is numerically favorable for MES-PIMD and then derive corresponding estimators in MES-PIMD for evaluating various physical properties. Furthermore, its application to several representative one-dimensional and multi-dimensional models demonstrates that MES-PIMD in principle offers a practical tool in either of the diabatic and adiabatic representations for studying exact quantum statistics of complex/large MES systems when the Born-Oppenheimer approximation, Condon approximation, and harmonic bath approximation are broken.},
doi = {10.1063/1.5005059},
journal = {Journal of Chemical Physics},
number = 10,
volume = 148,
place = {United States},
year = {Mon Nov 20 00:00:00 EST 2017},
month = {Mon Nov 20 00:00:00 EST 2017}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1063/1.5005059
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Cited by: 10 works
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Figures / Tables:

Table I Table I: Parameters [in Eq. (78)] for a two-electronic-state system coupled to a Morse oscillator [unit: atomic unit (a.u.)].
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      Figures / Tables found in this record:

      Table I (p. 3)table
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