Semiclassical Nonadiabatic Dynamics Using a Mixed Wave-Function Representation

Sophya V. Garashchuk, University of South Carolina - Columbia
V. A. Rassolov
G. C. Schatz

Copyright 2005 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics.

The following article appeared in

Garashchuk, S., Rassolov, V. A., & Schatz, G. C. (2005). Semiclassical nonadiabatic dynamics using a mixed wave-function representation. The Journal of Chemical Physics, 123, 174108.

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Nonadiabaticeffects 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 modelchemical reactions that demonstrate the capabilities of the method for various regimes of nonadiabaticdynamics.