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Title: Nonadiabatic quantum molecular dynamics with detailed balance

Abstract

In this paper, we present an approach for carrying out nonadiabatic molecular dynamics simulations of systems in which nonadiabatic transitions arise from the coupling between the classical atomic motions and a quasicontinuum of electronic quantum states. Such conditions occur in many research areas, including chemistry at metal surfaces, radiation damage of materials, and warm-dense-matter physics. The classical atomic motions are governed by stochastic Langevin-like equations, while the quantum electron dynamics is described by a master equation for the populations of the electronic states. These working equations are obtained from a first-principles derivation. Remarkably, unlike the widely used Ehrenfest and surface-hopping methods, the approach naturally satisfies the principle of detailed balance at equilibrium and therefore can describe the evolution to thermal equilibrium from an arbitrary initial state. Lastly, a practical algorithm is cast in the form of the widely used fewest-switches surface-hopping algorithm but with switching probabilities that are not specified ad hoc like in the standard algorithm but are instead derived.

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1483499
Alternate Identifier(s):
OSTI ID: 1481819
Report Number(s):
LA-UR-17-26600
Journal ID: ISSN 2469-9950; PRBMDO
Grant/Contract Number:  
89233218CNA000001; AC52-06NA25396; 20170490ER; 20170460ER
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 98; Journal Issue: 20; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Daligault, Jerome Olivier, and Mozyrsky, Dmitry. Nonadiabatic quantum molecular dynamics with detailed balance. United States: N. p., 2018. Web. doi:10.1103/PhysRevB.98.205120.
Daligault, Jerome Olivier, & Mozyrsky, Dmitry. Nonadiabatic quantum molecular dynamics with detailed balance. United States. doi:10.1103/PhysRevB.98.205120.
Daligault, Jerome Olivier, and Mozyrsky, Dmitry. Mon . "Nonadiabatic quantum molecular dynamics with detailed balance". United States. doi:10.1103/PhysRevB.98.205120.
@article{osti_1483499,
title = {Nonadiabatic quantum molecular dynamics with detailed balance},
author = {Daligault, Jerome Olivier and Mozyrsky, Dmitry},
abstractNote = {In this paper, we present an approach for carrying out nonadiabatic molecular dynamics simulations of systems in which nonadiabatic transitions arise from the coupling between the classical atomic motions and a quasicontinuum of electronic quantum states. Such conditions occur in many research areas, including chemistry at metal surfaces, radiation damage of materials, and warm-dense-matter physics. The classical atomic motions are governed by stochastic Langevin-like equations, while the quantum electron dynamics is described by a master equation for the populations of the electronic states. These working equations are obtained from a first-principles derivation. Remarkably, unlike the widely used Ehrenfest and surface-hopping methods, the approach naturally satisfies the principle of detailed balance at equilibrium and therefore can describe the evolution to thermal equilibrium from an arbitrary initial state. Lastly, a practical algorithm is cast in the form of the widely used fewest-switches surface-hopping algorithm but with switching probabilities that are not specified ad hoc like in the standard algorithm but are instead derived.},
doi = {10.1103/PhysRevB.98.205120},
journal = {Physical Review B},
number = 20,
volume = 98,
place = {United States},
year = {Mon Nov 12 00:00:00 EST 2018},
month = {Mon Nov 12 00:00:00 EST 2018}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on November 12, 2019
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