Curchod Basile F E, Glover William J, Martínez Todd J
Department of Chemistry, Durham University, South Road, Durham DH1 3LE, United Kingdom.
NYU Shanghai, 1555 Century Ave., Shanghai 200122, China.
J Phys Chem A. 2020 Jul 30;124(30):6133-6143. doi: 10.1021/acs.jpca.0c04113. Epub 2020 Jul 15.
multiple spawning provides a powerful and accurate way of describing the excited-state dynamics of molecular systems, whose strength resides in the proper description of coherence effects during nonadiabatic processes thanks to the coupling of trajectory basis functions. However, the simultaneous propagation of a large number of trajectory basis functions can be numerically inconvenient. We propose here an elegant and simple solution to this issue, which consists of (i) detecting uncoupled groups of coupled trajectory basis functions and (ii) selecting stochastically one of these groups to continue the multiple spawning dynamics. We show that this procedure can reproduce the results of full multiple spawning dynamics in cases where the uncoupled groups of trajectory basis functions stay uncoupled throughout the dynamics (which is often the case in high-dimensional problems). We present and discuss the aforementioned idea in detail and provide simple numerical applications on indole, ethylene, and protonated formaldimine, highlighting the potential of stochastic-selection multiple spawning.
多次生成提供了一种强大且准确的描述分子体系激发态动力学的方法，其优势在于通过轨迹基函数的耦合能够恰当地描述非绝热过程中的相干效应。然而，同时传播大量的轨迹基函数在数值计算上可能不太方便。我们在此提出一种针对此问题的简洁而优雅的解决方案，该方案包括：（i）检测耦合轨迹基函数的非耦合组；（ii）随机选择其中一组来继续多次生成动力学。我们表明，在轨迹基函数的非耦合组在整个动力学过程中保持非耦合的情况下（在高维问题中通常如此），此过程能够重现完全多次生成动力学的结果。我们详细阐述并讨论了上述想法，并在吲哚、乙烯和质子化甲亚胺上提供了简单的数值应用，突出了随机选择多次生成的潜力。
