Non-Born-Oppenheimer molecular dynamics of NaFH photodissociation

Ahren W. Jasper, Donald G. Truhlar

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The accuracy of non-Born-Oppenheimer (electronically nonadiabatic) semiclassical trajectory methods for simulations of "deep quantum" systems is reevaluated in light of recent quantum mechanical calculations of the photodissociation of the NaFH van der Waals complex. In contrast to the conclusion arrived at in an earlier study, semiclassical trajectory methods are shown to be qualitatively accurate for this system, thus further validating their use for systems with large electronic energy gaps. Product branching in semiclassical surface hopping and decay-of-mixing calculations is affected by a region of coupling where the excited state is energetically forbidden. Frustrated hops in this region may be attributed to a failure of the treatment of decoherence, and a stochastic model for decoherence is introduced into the surface hopping method and is shown to improve the agreement with the quantum mechanical results. A modification of the decay-of-mixing method resulting in faster decoherence in this region is shown to give similarly improved results.

Original languageEnglish (US)
Article number194306
JournalJournal of Chemical Physics
Issue number19
StatePublished - 2007

Bibliographical note

Funding Information:
This work was supported in part by the United States Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences and in part by the National Science Foundation through Grant No. CH07-04974.


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