Yu Le, Xu Chao, Lei Yibo, Zhu Chaoyuan, Wen Zhenyi
Institute of Molecular Science, Department of Applied Chemistry, and Center for Interdisciplinary Molecular Science, National Chiao-Tung University, Hsinchu 300, Taiwan.
Phys Chem Chem Phys. 2014 Dec 21;16(47):25883-95. doi: 10.1039/c4cp03498h. Epub 2014 Oct 29.
We develop a novel method to simulate analytical nonadiabatic switching probability based on effective coupling and effective collision energy by using only electronic adiabatic potential energy surfaces and its gradients in the case of avoided crossing types of nonadiabatic transitions. In addition, the present method can keep the same time step for computing both on-the-fly trajectory and nonadiabatic transitions accurately. The present method is most useful for localized nonadiabatic transitions induced by conical intersection. We employ the on-the-fly surface hopping algorithm with an ab initio quantum chemistry calculation to demonstrate a dynamic simulation for photoisomerization in azobenzene. Simulated quantum yield and lifetime converge to 0.39 and 53 femtosecond, respectively (0.33 and 0.81 picosecond) for cis-to-trans (trans-to-cis) photoisomerization with up to 800 (600) sampling trajectories. The present results agree well with those of the experiment, as well as results simulated with use of nonadiabatic coupling within Tully's fewest switching method. The present trajectory-based nonadiabatic molecular dynamics free from nonadiabatic coupling greatly enhances the simulation power of molecular dynamics for large complex chemical systems.
我们开发了一种新方法，仅利用电子绝热势能面及其梯度，在避免交叉型非绝热跃迁的情况下，基于有效耦合和有效碰撞能量来模拟解析非绝热开关概率。此外，该方法在精确计算实时轨迹和非绝热跃迁时可以保持相同的时间步长。该方法对于由锥形交叉诱导的局域非绝热跃迁最为有用。我们采用实时表面跳跃算法结合从头算量子化学计算来演示偶氮苯光异构化的动态模拟。对于顺 - 反（反 - 顺）光异构化，使用多达800（600）个采样轨迹时，模拟的量子产率和寿命分别收敛到0.39和53飞秒（0.33和0.81皮秒）。目前的结果与实验结果以及使用塔利最少开关方法中的非绝热耦合模拟的结果吻合得很好。这种基于轨迹的无绝热耦合的非绝热分子动力学极大地增强了对大型复杂化学系统分子动力学的模拟能力。
