Semiclassical nonadiabatic dynamics using a mixed wave-function representation

Sophya Garashchuk, Vitaly A. Rassolov, George C Schatz

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

Nonadiabatic effects in quantum dynamics are described using a mixed polar/coordinate space representation of the wave function. The polar part evolves on dynamically determined potential surfaces that have diabatic and adiabatic potentials as limiting cases of weak localized and strong extended diabatic couplings. The coordinate space part, generalized to a matrix form, describes transitions between the surfaces. Choice of the effective potentials for the polar part and partitioning of the wave function enables one to represent the total wave function in terms of smooth components that can be accurately propagated semiclassically using the approximate quantum potential and small basis sets. Examples are given for two-state one-dimensional problems that model chemical reactions that demonstrate the capabilities of the method for various regimes of nonadiabatic dynamics.

Original languageEnglish
Article number174108
JournalJournal of Chemical Physics
Volume123
Issue number17
DOIs
Publication statusPublished - Nov 1 2005

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Wave functions
wave functions
polar coordinates
Chemical reactions
chemical reactions
matrices

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Semiclassical nonadiabatic dynamics using a mixed wave-function representation. / Garashchuk, Sophya; Rassolov, Vitaly A.; Schatz, George C.

In: Journal of Chemical Physics, Vol. 123, No. 17, 174108, 01.11.2005.

Research output: Contribution to journalArticle

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