An analysis of the accuracy of an initial value representation surface hopping wave function in the interaction and asymptotic regions.
The behavior of an initial value representation surface hopping wave function is examined. Since this method is an initial value representation for the semiclassical solution of the time independent Schrodinger equation for nonadiabatic problems, it has computational advantages over the primitive surface hopping wave function. The primitive wave function has been shown to provide transition probabilities that accurately compare with quantum results for model problems. The analysis presented in this work shows that the multistate initial value representation surface hopping wave function should approach the primitive result in asymptotic regions and provide transition probabilities with the same level of accuracy for scattering problems as the primitive method.
Sergeev
Alexey
A
Department of Chemistry, Tulane University, New Orleans, LA 70118, USA.
Herman
Michael F
MF