Mixed quantum-classical equilibrium in global flux surface hopping

Global flux surface hopping (GFSH) generalizes fewest switches surface hopping (FSSH)—one of the most popular approaches to nonadiabatic molecular dynamics—for processes exhibiting superexchange. We show that GFSH satisfies detailed balance and leads to thermodynamic equilibrium with accuracy simila...

Full description

Saved in:
Bibliographic Details
Published in:The Journal of chemical physics 2015-06, Vol.142 (22), p.224102-224102
Main Authors: Sifain, Andrew E, Wang, Linjun, Prezhdo, Oleg V
Format: Article
Language:English
Subjects:
ACCURACY
ATOMS
ELECTRONS
Equilibrium
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
MAGNETIC SURFACES
Molecular dynamics
MOLECULAR DYNAMICS METHOD
PHONONS
QUANTUM SYSTEMS
Quantum theory
RELAXATION
SURFACES
Switches
THERMAL EQUILIBRIUM
Thermodynamic equilibrium
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Global flux surface hopping (GFSH) generalizes fewest switches surface hopping (FSSH)—one of the most popular approaches to nonadiabatic molecular dynamics—for processes exhibiting superexchange. We show that GFSH satisfies detailed balance and leads to thermodynamic equilibrium with accuracy similar to FSSH. This feature is particularly important when studying electron-vibrational relaxation and phonon-assisted transport. By studying the dynamics in a three-level quantum system coupled to a classical atom in contact with a classical bath, we demonstrate that both FSSH and GFSH achieve the Boltzmann state populations. Thermal equilibrium is attained significantly faster with GFSH, since it accurately represents the superexchange process. GFSH converges closer to the Boltzmann averages than FSSH and exhibits significantly smaller statistical errors.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4922162