Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, Pennsylvania 19104, USA.
J Chem Phys. 2013 Dec 7;139(21):211101. doi: 10.1063/1.4837795.
In a recent paper, we presented a road map for how Tully's fewest switches surface hopping (FSSH) algorithm can be derived, under certain circumstances, from the mixed quantum-classical Liouville equation. In this communication, we now demonstrate how this new interpretation of surface hopping can yield significantly enhanced results for electronic properties in nonadiabatic calculations. Specifically, we calculate diabatic populations for the spin-boson problem using FSSH trajectories. We show that, for some Hamiltonians, without changing the FSSH algorithm at all but rather simply reinterpreting the ensemble of surface hopping trajectories, we recover excellent results and remove any and all ambiguity about the initial condition problem.
在最近的一篇论文中，我们提出了一个路线图，说明在某些情况下，如何从混合量子经典刘维尔方程推导出塔利的最少切换表面跳跃（FSSH）算法。在本通讯中，我们现在展示这种新的表面跳跃解释如何为非绝热计算中的电子性质带来显著增强的结果。具体来说，我们使用 FSSH 轨迹计算自旋-玻色子问题的非绝热人口。我们表明，对于某些哈密顿量，我们无需更改 FSSH 算法，而只需重新解释表面跳跃轨迹的集合，就可以恢复出色的结果，并消除初始条件问题的任何和所有歧义。
