skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Trajectory-adjusted electronic zero point energy in classical Meyer-Miller vibronic dynamics: Symmetrical quasiclassical application to photodissociation

Abstract

An electronic zero-point energy (ZPE) adjustment protocol is proposed within the context of the symmetrical quasiclassical (SQC) quantization of the electronic oscillator degrees of freedom (DOF) in classical Meyer-Miller (MM) vibronic dynamics for the molecular dynamics treatment of electronically nonadiabatic processes. The “adjustment” procedure maintains the same initial and final distributions of coordinates and momenta in the electronic oscillator DOF as previously given by the SQC windowing protocol but modifies the ZPE parameter in the MM Hamiltonian, on a per trajectory basis, so that the initial nuclear forces are precisely those corresponding to the initial electronic quantum state. Examples demonstrate that this slight modification to the standard SQC/MM approach greatly improves treatment of the multistate nonadiabatic dynamics following a Franck-Condon type vertical excitation onto a highly repulsive potential energy surface as is typical in the photodissociation context.

Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1577592
Alternate Identifier(s):
OSTI ID: 1514746
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 19; 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

Citation Formats

Trajectory-adjusted electronic zero point energy in classical Meyer-Miller vibronic dynamics: Symmetrical quasiclassical application to photodissociation. United States: N. p., 2019. Web. https://doi.org/10.1063/1.5094458.
Trajectory-adjusted electronic zero point energy in classical Meyer-Miller vibronic dynamics: Symmetrical quasiclassical application to photodissociation. United States. https://doi.org/10.1063/1.5094458
Mon . "Trajectory-adjusted electronic zero point energy in classical Meyer-Miller vibronic dynamics: Symmetrical quasiclassical application to photodissociation". United States. https://doi.org/10.1063/1.5094458. https://www.osti.gov/servlets/purl/1577592.
@article{osti_1577592,
title = {Trajectory-adjusted electronic zero point energy in classical Meyer-Miller vibronic dynamics: Symmetrical quasiclassical application to photodissociation},
author = {None, None},
abstractNote = {An electronic zero-point energy (ZPE) adjustment protocol is proposed within the context of the symmetrical quasiclassical (SQC) quantization of the electronic oscillator degrees of freedom (DOF) in classical Meyer-Miller (MM) vibronic dynamics for the molecular dynamics treatment of electronically nonadiabatic processes. The “adjustment” procedure maintains the same initial and final distributions of coordinates and momenta in the electronic oscillator DOF as previously given by the SQC windowing protocol but modifies the ZPE parameter in the MM Hamiltonian, on a per trajectory basis, so that the initial nuclear forces are precisely those corresponding to the initial electronic quantum state. Examples demonstrate that this slight modification to the standard SQC/MM approach greatly improves treatment of the multistate nonadiabatic dynamics following a Franck-Condon type vertical excitation onto a highly repulsive potential energy surface as is typical in the photodissociation context.},
doi = {10.1063/1.5094458},
journal = {Journal of Chemical Physics},
number = 19,
volume = 150,
place = {United States},
year = {2019},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

A symmetrical quasi-classical windowing model for the molecular dynamics treatment of non-adiabatic processes involving many electronic states
journal, March 2019

  • Cotton, Stephen J.; Miller, William H.
  • The Journal of Chemical Physics, Vol. 150, Issue 10
  • DOI: 10.1063/1.5087160

A classical analog for electronic degrees of freedom in nonadiabatic collision processes
journal, April 1979

  • Meyera), Hans‐Dieter; Miller, William H.
  • The Journal of Chemical Physics, Vol. 70, Issue 7
  • DOI: 10.1063/1.437910

Symmetrical windowing for quantum states in quasi-classical trajectory simulations: Application to electronically non-adiabatic processes
journal, December 2013

  • Cotton, Stephen J.; Miller, William H.
  • The Journal of Chemical Physics, Vol. 139, Issue 23
  • DOI: 10.1063/1.4845235

Classical molecular dynamics simulation of electronically non-adiabatic processes
journal, January 2016

  • Miller, William H.; Cotton, Stephen J.
  • Faraday Discussions, Vol. 195
  • DOI: 10.1039/c6fd00181e

Semi-classical path integral non-adiabatic dynamics: a partial linearized classical mapping Hamiltonian approach
journal, May 2012


Symmetrical Windowing for Quantum States in Quasi-Classical Trajectory Simulations
journal, March 2013

  • Cotton, Stephen J.; Miller, William H.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 32
  • DOI: 10.1021/jp401078u

A new symmetrical quasi-classical model for electronically non-adiabatic processes: Application to the case of weak non-adiabatic coupling
journal, October 2016

  • Cotton, Stephen J.; Miller, William H.
  • The Journal of Chemical Physics, Vol. 145, Issue 14
  • DOI: 10.1063/1.4963914

Simulating Excited State Dynamics in Systems with Multiple Avoided Crossings Using Mapping Variable Ring Polymer Molecular Dynamics
journal, October 2015


Semiclassical Description of Nonadiabatic Quantum Dynamics
journal, January 1997


An assessment of mean-field mixed semiclassical approaches: Equilibrium populations and algorithm stability
journal, April 2016

  • Bellonzi, Nicole; Jain, Amber; Subotnik, Joseph E.
  • The Journal of Chemical Physics, Vol. 144, Issue 15
  • DOI: 10.1063/1.4946810

    Works referencing / citing this record:

    Initial sampling in symmetrical quasiclassical dynamics based on Li–Miller mapping Hamiltonian
    journal, January 2019

    • Zheng, Jie; Xie, Yu; Jiang, Shengshi
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 48
    • DOI: 10.1039/c9cp03975a

    Special topic on dynamics of open quantum systems
    journal, January 2020

    • Berkelbach, Timothy C.; Thoss, Michael
    • The Journal of Chemical Physics, Vol. 152, Issue 2
    • DOI: 10.1063/1.5142731