Li Guijie, Shi Zhecun, Guo Xin, Wang Linjun
Key Laboratory of Excited-State Materials of Zhejiang Province, Department of Chemistry, Zhejiang University, Hangzhou 310058, China.
J Phys Chem Lett. 2023 Nov 9;14(44):9855-9863. doi: 10.1021/acs.jpclett.3c02690. Epub 2023 Oct 27.
When the traditional Ehrenfest mean field approach is employed to simulate nonadiabatic dynamics, an effective wave packet (WP) on the average potential energy surface (PES) is utilized to describe the nuclear motion. In the fully quantum picture, however, the WP components on different adiabatic PESs gradually separate in space because they evolve under different velocities and forces. Due to trajectory branching of the WP components, proper decoherence needs to be taken into account, and the spatial distribution of population cannot be described by a single effective WP. Here, we propose an auxiliary branching corrected mean field (A-BCMF) method, where trajectories of auxiliary WPs on adiabatic PESs are introduced. As benchmarked in the three standard Tully models, A-BCMF not only gives correct channel populations but also captures an accurate time-dependent spatial distribution of population. Thereby, we reveal the important role of auxiliary WPs in solving intrinsic problems of the widely used mean field description of nonadiabatic dynamics.
