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Title: Coupled wave-packets for non-adiabatic molecular dynamics: a generalization of Gaussian wave-packet dynamics to multiple potential energy surfaces

Accurate simulation of the non-adiabatic dynamics of molecules in excited electronic states is key to understanding molecular photo-physical processes. Here we present a novel method, based on a semiclassical approximation, that is as efficient as the commonly used mean field Ehrenfest or ad hoc surface hopping methods and properly accounts for interference and decoherence effects. This novel method is an extension of Heller's thawed Gaussian wave-packet dynamics that includes coupling between potential energy surfaces. By studying several standard test problems we demonstrate that the accuracy of the method can be systematically improved while maintaining high efficiency. The method is suitable for investigating the role of quantum coherence in the non-adiabatic dynamics of many-atom molecules.
Authors:
 [1] ;  [2] ;  [3]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Theoretical Division, Center for Nonlinear Studies
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Theoretical Division, Center for Nonlinear Studies and Center for Integrated Nanotechnologies
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Theoretical Division
Publication Date:
Report Number(s):
LA-UR-16-20319
Journal ID: ISSN 2041-6520
Grant/Contract Number:
AC52-06NA25396
Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 7; Journal Issue: 8; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Inorganic and Physical Chemistry
OSTI Identifier:
1338745

White, Alexander James, Tretiak, Sergei, and Mozyrsky, Dima V. Coupled wave-packets for non-adiabatic molecular dynamics: a generalization of Gaussian wave-packet dynamics to multiple potential energy surfaces. United States: N. p., Web. doi:10.1039/C6SC01319H.
White, Alexander James, Tretiak, Sergei, & Mozyrsky, Dima V. Coupled wave-packets for non-adiabatic molecular dynamics: a generalization of Gaussian wave-packet dynamics to multiple potential energy surfaces. United States. doi:10.1039/C6SC01319H.
White, Alexander James, Tretiak, Sergei, and Mozyrsky, Dima V. 2016. "Coupled wave-packets for non-adiabatic molecular dynamics: a generalization of Gaussian wave-packet dynamics to multiple potential energy surfaces". United States. doi:10.1039/C6SC01319H. https://www.osti.gov/servlets/purl/1338745.
@article{osti_1338745,
title = {Coupled wave-packets for non-adiabatic molecular dynamics: a generalization of Gaussian wave-packet dynamics to multiple potential energy surfaces},
author = {White, Alexander James and Tretiak, Sergei and Mozyrsky, Dima V.},
abstractNote = {Accurate simulation of the non-adiabatic dynamics of molecules in excited electronic states is key to understanding molecular photo-physical processes. Here we present a novel method, based on a semiclassical approximation, that is as efficient as the commonly used mean field Ehrenfest or ad hoc surface hopping methods and properly accounts for interference and decoherence effects. This novel method is an extension of Heller's thawed Gaussian wave-packet dynamics that includes coupling between potential energy surfaces. By studying several standard test problems we demonstrate that the accuracy of the method can be systematically improved while maintaining high efficiency. The method is suitable for investigating the role of quantum coherence in the non-adiabatic dynamics of many-atom molecules.},
doi = {10.1039/C6SC01319H},
journal = {Chemical Science},
number = 8,
volume = 7,
place = {United States},
year = {2016},
month = {4}
}