Geometric phase effects on transition-state resonances and bound vibrational states of H3 via a time-dependent wavepacket method

Abstract

A time-dependent wavepacket method for including geometric phase (GP) effects in hyperspherical coordinates is given. It uses the hybrid basis/grid representation and prime-factor fast Fourier transformation (PFFT) technique to propagate a wavepacket while the GP effects are treated on the fly using the method of Billing and Marković (J. Chem. Phys., 1993, 99, 2674). The calculated vibrational states of the first electronically excited H ₃ molecule with and without GP effects are found to be significantly different and in excellent agreement with previous theoretical investigations. In contrast, GP effects on transition-state resonances of ground-state H ₃ are minor, although some notable differences can be observed in the autocorrelation functions after 90 fs wavepacket propagation.