New implementation of the trajectory surface hopping method with use of the Zhu–Nakamura theory. II. Application to the charge transfer processes in the 3D DH2+ system

Abstract

The newly implemented trajectory surface hopping (TSH) method for the collinear system with use of the Zhu–Nakamura semiclassical theory of nonadiabatic transition [C. Zhu, K. Nobusada, and H. Nakamura, J. Chem. Phys. 115, 3031 (2001)] is extended to treat 3D nonadiabatic reactions. Since the avoided crossing seam becomes a two-dimensional surface in the 3D system, the nonadiabatic transition region and the possibility of classically forbidden hops are enlarged very much in comparison with those in the collinear case. As a result, the contribution of the classically forbidden hops is quite a bit enhanced in the 3D system. Conservation of total angular momentum J is taken into account by slightly rotating the direction of momentum during the hop in the classically forbidden case. The method is tested by applying to the charge transfer processes in the 3D DH2+ system for J=0. Numerical results clearly demonstrate that the new TSH method works very well at all energies and for all initial vibrational states considered compared to the old TSH method based on the Landau–Zener formula. The significant discrepancy between the two TSH methods survives even at high collision energy and high vibrational states in contrast to the collinear case, indicating the importance of the classically forbidden hops in 3D systems. The new TSH method is considered to be a very promising method to deal with high dimensional nonadiabatic dynamics. It should also be noted that the new TSH method does not require any knowledge of nonadiabatic coupling and is based only on adiabatic potentials.