发布时间：

2025-04-30

论文名称：

Performance of TDDFT with and without spin-flip in trajectory surface hopping dynamics: Cis-trans azobenzene photoisomerization

发表刊物：

Physical Chemistry Chemical Physics

摘要：

Time-dependent density functional theory (TDDFT) with and without spin-flip scheme is extensively compared in on-the-fly trajectory surface hopping molecular dynamics with global switching (GS) algorithm. Simulation is performed for the cis-trans azobenzene photoisomerization following excitation to the S1(nπ*) state that involves in conical intersection (CI) between ground and the first excited states. This CI is found as correctly single-cone (artificial double-cone) structure computed by TDDFT method with (without) spin-flip. Nevertheless, simulated quantum yields and lifetimes are in very good agreement; 0.43 and 63fs (0.34 and 62fs) for cis-to-trans isomerization, and 0.11 and 2200fs (0.13 and 1040fs) for trans-to-cis isomerization, by TDDFT with (without) spin-flip scheme. Distributions of excited-state decay, hopping spots and products, as well as typical trajectories have similar patterns and behaviors with and without spin-flip. The global switching trajectory surface hopping method is demonstrated well suitable with TDDFT on-the-fly dynamic simulation with and without spin-flip. For comparison, the previous simulation with CASSCF method and Tully’s fewest-switches trajectory surface hopping method are also addressed.

合写作者：

Yue, L.; Liu, Y.-J.; Zhu, C. Y.

卷号：

20(37)

页面范围：

24123-24139

是否译文：

否

发表时间：

2018-08-28