Classical and nonclassical effects in surface hopping methodology for simulating coupled electronic-nuclear dynamics
Classical and nonclassical effects in surface hopping methodology for simulating coupled electronic-nuclear dynamics
复制标题
模拟耦合电子核动力学的表面跳跃方法中的经典和非经典效应
DOI：
10.1039/c9fd00042a
复制
发表时间：
2019
影响因子：
3.4
通讯作者：
Martens, Craig C.
中科院分区：
文献类型：
--
作者：
Martens, Craig C.
在本文中，我们分析了两种模拟电子跃迁分子动力学的替代方法的详细量子经典行为：流行的最少开关表面跳跃（FSSH）方法，由 Tully 于 1990 年提出 [Tully, J. Chem. Phys., 1990, 93, 1061] 和我们最近开发的量子轨迹表面跳跃 (QTSH) 方法 [Martens, J. Phys.化学。 A, 2019, 123, 1110]。两种方法都采用独立的轨迹集合，在电子表面之间进行随机转变。这些方法在能量守恒的处理上有所不同，FSSH 在发生表面跳跃时通过重新调整经典动量来强制经典动能和势能守恒，而 QTSH 在整个动力学过程中结合了量子力，这自然导致了完整的量子经典能量的守恒。我们研究了几个简单模型系统的表面跳跃方法的群体转移和能量预算，并与精确的量子结果进行了比较。此外，还将相空间中轨迹系综的详细动力学与维格纳表示中的量子演化进行了比较。得出结论。
In this paper, we analyze the detailed quantum-classical behavior of two alternative approaches to simulating molecular dynamics with electronic transitions: the popular fewest switches surface hopping (FSSH) method, introduced by Tully in 1990 [Tully, J. Chem. Phys., 1990, 93, 1061] and our recently developed quantum trajectory surface hopping (QTSH) method [Martens, J. Phys. Chem. A, 2019, 123, 1110]. Both approaches employ an independent ensemble of trajectories that undergo stochastic transitions between electronic surfaces. The methods differ in their treatment of energy conservation, with FSSH imposing conservation of the classical kinetic plus potential energy by rescaling the classical momentum when a surface hop occurs while QTSH incorporates a quantum force throughout the dynamics which leads naturally to the conservation of the full quantum-classical energy. We investigate the population transfer and energy budget of the surface hopping methods for several simple model systems and compare with exact quantum results. In addition, the detailed dynamics of the trajectory ensembles in phase space are compared with the quantum evolution in the Wigner representation. Conclusions are drawn.