A singularity free surface hopping expansion for the multistate wave function.
A version of a surface hopping wave function for nonadiabatic multistate problems, which is free of turning point singularities, is derived and tested. The primitive semiclassical form of the particular surface hopping method considered has been shown to be highly accurate, even for classically forbidden processes. However, this semiclassical wave function displays the usual singular behavior at turning points and caustics in the classical motion. Numerical data has shown that this somewhat reduces its accuracy when the energy is near the crossing energy of the diabatic electronic surfaces. The singularity free version of this surface hopping wave function is derived by partitioning the x-axis into a large number of small steps for one dimensional problems. The adiabatic electronic energy surfaces are approximated to be linear functions within each step. The matching conditions required by the continuity of the wave function and its derivative at each step boundary provide the needed conditions to obtain the amplitudes for changes in electronic state and/or reflection of the trajectory for the motion of the nuclei. This leads to a form of the surface hopping wave function that is free of turning point singularities. The method is tested for a one dimensional model problem, and it is found to be highly accurate at all energies considered, even when the energy is near the crossing energy.
Herman
Michael F
MF
Department of Chemistry, Tulane University, New Orleans, Louisiana 70118, USA. mherman@tulane.edu