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

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/1.5005059 · OSTI ID:1498058
 [1]; ORCiD logo [1]
  1. Peking Univ., Beijing (China). Beijing National Laboratory for Molecular Sciences, Institute of Theoretical and Computational Chemistry, College of Chemistry and Molecular Engineering
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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.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1498058
Journal Information:
Journal of Chemical Physics, Vol. 148, Issue 10; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (5)

Preface: Special Topic on Nuclear Quantum Effects journal March 2018
A new perspective for nonadiabatic dynamics with phase space mapping models journal July 2019
Critical role of quantum dynamical effects in the Raman spectroscopy of liquid water journal November 2017
Critical role of quantum dynamical effects in the Raman spectroscopy of liquid water text January 2018
Critical role of quantum dynamical effects in the Raman spectroscopy of liquid water text January 2017

Figures / Tables (20)

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