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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4963914· OSTI ID:1377537
 [1];  [1]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry. Center for Theoretical Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
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Previous work has shown how a symmetrical quasi-classical (SQC) windowing procedure can be used to quantize the initial and final electronic degrees of freedom in the Meyer-Miller (MM) classical vibronic (i.e, nuclear + electronic) Hamiltonian, and that the approach provides a very good description of electronically non-adiabatic processes within a standard classical molecular dynamics framework for a number of benchmark problems. This study explores application of the SQC/MM approach to the case of very weak non-adiabatic coupling between the electronic states, showing (as anticipated) how the standard SQC/MM approach used to date fails in this limit, and then devises a new SQC windowing scheme to deal with it. Finally, application of this new SQC model to a variety of realistic benchmark systems shows that the new model not only treats the weak coupling case extremely well, but it is also seen to describe the “normal” regime (of electronic transition probabilities ≳ 0.1) even more accurately than the previous “standard” model.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
National Science Foundation (NSF) (United States); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1377537
Alternate ID(s):
OSTI ID: 1328956
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 14 Vol. 145; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (19)

Classical molecular dynamics simulation of electronically non-adiabatic processes journal January 2016
Combining Meyer–Miller Hamiltonian with electronic structure methods for on-the-fly nonadiabatic dynamics simulations: implementation and application journal January 2019
Initial sampling in symmetrical quasiclassical dynamics based on Li–Miller mapping Hamiltonian journal January 2019
On the adiabatic representation of Meyer-Miller electronic-nuclear dynamics journal August 2017
A walk through the approximations of ab initio multiple spawning journal April 2018
Communication: Symmetrical quasi-classical analysis of linear optical spectroscopy journal May 2018
The symmetrical quasi-classical approach to electronically nonadiabatic dynamics applied to ultrafast exciton migration processes in semiconducting polymers journal July 2018
Performance evaluation of the symmetrical quasi-classical dynamics method based on Meyer-Miller mapping Hamiltonian in the treatment of site-exciton models journal November 2018
A modified approach for simulating electronically nonadiabatic dynamics via the generalized quantum master equation journal January 2019
A symmetrical quasi-classical windowing model for the molecular dynamics treatment of non-adiabatic processes involving many electronic states journal March 2019
Trajectory-adjusted electronic zero point energy in classical Meyer-Miller vibronic dynamics: Symmetrical quasiclassical application to photodissociation journal May 2019
State dependent ring polymer molecular dynamics for investigating excited nonadiabatic dynamics journal June 2019
Spin-mapping approach for nonadiabatic molecular dynamics journal July 2019
A new perspective for nonadiabatic dynamics with phase space mapping models journal July 2019
Combining the mapping Hamiltonian linearized semiclassical approach with the generalized quantum master equation to simulate electronically nonadiabatic molecular dynamics journal August 2019
Mixed quantum-classical electrodynamics: Understanding spontaneous decay and zero-point energy journal March 2018
Spin-mapping approach for nonadiabatic molecular dynamics text January 2019
Performance Evaluation of the Symmetrical Quasi-Classical Dynamics Method based on Meyer-Miller Mapping Hamiltonian in the Treatment of Site-Exciton Models text January 2018
Initial Sampling in Symmetrical Quasiclassical Dynamics Based on Li-Miller Mapping Hamiltonian text January 2018

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Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
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