Critical appraisal of the fewest switches algorithm for surface hopping
Critical appraisal of the fewest switches algorithm for surface hopping
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DOI：
10.1063/1.2715585
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发表时间：
2007-04-07
影响因子：
4.4
通讯作者：
Persico, Maurizio
中科院分区：
文献类型：
--
作者：
Granucci, Giovanni;Persico, Maurizio
本文讨论了弹道表面跳跃方法中的内部一致性问题，即在对所有弹道进行平均后，要求在每个电子态上运行的弹道分数等于由含时电子薛定谔方程计算的概率。他们根据塔利“开关最少”的精神，推导出了一个跳跃概率的公式，这将产生一个严格一致的治疗方法。它们显示了塔利广泛使用的表面跳跃算法与单独运行每条轨迹时不能应用的“精确”处方之间的关系。它们还指出了一致性问题与电子波函数的相干传播以及弱耦合区态几率的相干Rabi型振荡引起的伪影之间的联系。一个真实的分子(偶氮苯)和两个特设模型作为例子来说明上述理论论点。根据特鲁拉尔的小组[朱，J.化学]的建议。太棒了。121,7658(2004)朱，J.化学。理论计算。1,527(2005)]，他们结合Tully算法对态概率进行退相干修正，在内部一致性方面获得了令人满意的结果，并与量子波包计算的结果相一致。(C)2007年美国物理研究所。
In this paper the authors address the problem of internal consistency in trajectory surface hopping methods, i.e., the requirement that the fraction of trajectories running on each electronic state equals the probabilities computed by the electronic time-dependent Schrodinger equation, after averaging over all trajectories. They derive a formula for the hopping probability in Tully's "fewest switches" spirit that would yield a rigorously consistent treatment. They show the relationship of Tully's widely used surface hopping algorithm with the "exact" prescription that cannot be applied when running each trajectory independently. They also bring out the connection of the consistency problem with the coherent propagation of the electronic wave function and the artifacts caused by coherent Rabi-type oscillations of the state probabilities in weak coupling regimes. A real molecule (azobenzene) and two ad hoc models serve as examples to illustrate the above theoretical arguments. Following a proposal by Truhlar's group [Zhu , J. Chem. Phys. 121, 7658 (2004) Zhu , J. Chem. Theory Comput. 1, 527 (2005)], they apply a decoherence correction to the state probabilities, in conjunction with Tully's algorithm, and they obtain satisfactory results in terms of internal consistency and of agreement with the outcomes of quantum wave packet calculations. (c) 2007 American Institute of Physics.