title: Restoring electronic coherence/decoherence for a trajectory-based nonadiabatic molecular dynamics.
abstract: By utilizing the time-independent semiclassical phase integral, we obtained modified coupled time-dependent Schrödinger equations that restore coherences and induce decoherences within original simple trajectory-based nonadiabatic molecular dynamic algorithms. Nonadiabatic transition probabilities simulated from both Tully's fewest switches and semiclassical Ehrenfest algorithms follow exact quantum electronic oscillations and amplitudes for three out of the four well-known model systems. Within the present theory, nonadiabatic transitions estimated from statistical ensemble of trajectories accurately follow those of the modified electronic wave functions. The present theory can be immediately applied to the molecular dynamic simulations of photochemical and photophysical processes involving electronic excited states.
authors.affiliation: Institute of Molecular Science, Department of Applied Chemistry, and Center for Interdisciplinary Molecular Science, National Chiao-Tung University, Hsinchu 300, Taiwan.|State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Science, Zhongshan Road 457, Dalian 116023, P. R. China.
authors.forename: Chaoyuan
authors.initials: C
authors.lastname: Zhu