A new symmetrical quasi-classical model for electronically non-adiabatic processes: Application to the case of weak non-adiabatic coupling
- 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
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:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- Grant/Contract Number:
- AC02-05CH11231; CHE-1464647
- OSTI ID:
- 1377537
- Alternate ID(s):
- OSTI ID: 1328956
- Journal Information:
- Journal of Chemical Physics, Vol. 145, Issue 14; ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
Web of Science
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