Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.5094458· OSTI ID:1577592
 [1];  [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
+ Show Author Affiliations
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.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1577592
Alternate ID(s):
OSTI ID: 1514746
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 19 Vol. 150; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (13)

Ultrafast non-adiabatic dynamics of systems with multiple surface crossings: a test of the Meyer–Miller Hamiltonian with semiclassical initial value representation methods journal December 2001
Simulating Excited State Dynamics in Systems with Multiple Avoided Crossings Using Mapping Variable Ring Polymer Molecular Dynamics journal October 2015
Coherence-Controlled Nonadiabatic Dynamics via State-Space Decomposition: A Consistent Way To Incorporate Ehrenfest and Born–Oppenheimer-Like Treatments of Nuclear Motion journal October 2016
Symmetrical Windowing for Quantum States in Quasi-Classical Trajectory Simulations journal March 2013
Classical molecular dynamics simulation of electronically non-adiabatic processes journal January 2016
A classical analog for electronic degrees of freedom in nonadiabatic collision processes journal April 1979
Symmetrical windowing for quantum states in quasi-classical trajectory simulations: Application to electronically non-adiabatic processes journal December 2013
An assessment of mean-field mixed semiclassical approaches: Equilibrium populations and algorithm stability journal April 2016
Communication: Wigner functions in action-angle variables, Bohr-Sommerfeld quantization, the Heisenberg correspondence principle, and a symmetrical quasi-classical approach to the full electronic density matrix journal August 2016
A new symmetrical quasi-classical model for electronically non-adiabatic processes: Application to the case of weak non-adiabatic coupling journal October 2016
A symmetrical quasi-classical windowing model for the molecular dynamics treatment of non-adiabatic processes involving many electronic states journal March 2019
Semi-classical path integral non-adiabatic dynamics: a partial linearized classical mapping Hamiltonian approach journal May 2012
Semiclassical Description of Nonadiabatic Quantum Dynamics journal January 1997

Cited By (3)

Initial sampling in symmetrical quasiclassical dynamics based on Li–Miller mapping Hamiltonian journal January 2019
Special topic on dynamics of open quantum systems journal January 2020
Initial Sampling in Symmetrical Quasiclassical Dynamics Based on Li-Miller Mapping Hamiltonian text January 2018

Similar Records

A Symmetrical Quasi-Classical Spin-Mapping Model for the Electronic Degrees of Freedom in Non-Adiabatic Processes
Journal Article · Mon Aug 24 00:00:00 EDT 2015 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory · OSTI ID:1378696
On the adiabatic representation of Meyer-Miller electronic-nuclear dynamics
Journal Article · Thu Aug 10 20:00:00 EDT 2017 · Journal of Chemical Physics · OSTI ID:1543838
Classical model for laser-induced nonadiabatic collision processes
Journal Article · Tue Jul 01 00:00:00 EDT 1980 · J. Chem. Phys.; (United States) · OSTI ID:5364837

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Classical trajectory method
Molecular dynamics
Non-adiabatic molecular dynamics
Photodissociation
Potential energy surfaces
Quantum algorithms
Quantum chemical dynamics
Quantum effects
Zero point energy