Optimal representation for semiclassical surface hopping methods
Optimal representation for semiclassical surface hopping methods
复制标题
半经典表面跳跃方法的最佳表示
DOI：
10.1063/1.478298
复制
发表时间：
1999
影响因子：
4.4
通讯作者：
Michael F. Herman
中科院分区：
文献类型：
--
作者：
Michael F. Herman
给出了传播子的半经典表面跳跃展开式，用来描述“快”可变量子态。该表象可以是绝热或非绝热表象，也可以是介于这两者之间的任何表象。定义了一种特定的表示法，它在最小化集成的州际耦合的意义上是最优的。在这个定义中，耦合是在合适的经典轨道上积分的。对一个简单的一维曲线穿越模型问题的计算表明，使用这种最优表示法可以显著降低多跳项在展开中的重要性。给出了这种最优表示的一种近似形式，其数值实现要简单得多。对模型曲线交叉问题的计算表明，这种近似最优表示提供的集成耦合非常接近于最优表示所获得的耦合。这些结果表明，这一近似最优的。
A semiclassical surface hopping expansion of the propagator is developed for a general representation of the “fast” variable quantum states. The representation can be the adiabatic or diabatic representation or any representation between these two. A particular representation is defined, which is optimal in the sense that it minimizes the integrated interstate coupling. The coupling is integrated over a suitable classical trajectory in this definition. Calculations for a simple one-dimensional curve crossing model problem show that the use of this optimal representation can significantly reduce the importance of multihop terms in the expansion. An approximation to this optimal representation is proposed, which is much simpler to implement numerically. Calculations for the model curve crossing problem demonstrate that this approximate optimal representation provides integrated couplings that are very close to those obtained for the optimal representation. These results suggest that this approximate optimal...