Zhou Jian-Ge, Shu Yinan, Michaels Brianna, Yang Shan, Prezhdo Oleg
Interdisciplinary Nanotoxicity Center, Department of Chemistry, Physics and Atmospheric Sciences, Jackson State University, Jackson, Mississippi 39217, United States.
Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455-0431, United States.
J Phys Chem Lett. 2025 Apr 10;16(14):3473-3482. doi: 10.1021/acs.jpclett.5c00625. Epub 2025 Mar 29.
We propose the generalized initial velocity sampling algorithm at a transition state, in which the total initial kinetic energy and extra positive initial velocity along the reaction coordinate have been introduced to improve the accuracy and efficiency of nonadiabatic dynamics simulation. This sampling algorithm is very useful for chemical reactions with multiple transition states, e.g., two transition states in the thermolysis of four-membered heterocyclic peroxides. The dependence of the chemiexcitation yields, dissociation times, and other quantities on the total initial kinetic energy and extra positive initial velocity has been investigated. By taking different CASPT2 corrections and additional positive initial velocities into account, we found that the resulting triplet quantum yield matches the experimental result perfectly. In most ensembles, the secondary primary intersystem crossing, i.e., the first singlet excited state to the first triplet state, is a major direct production channel for the first triplet state product trajectories.
我们提出了一种处于过渡态的广义初始速度采样算法，其中引入了总初始动能和沿反应坐标的额外正初始速度，以提高非绝热动力学模拟的准确性和效率。这种采样算法对于具有多个过渡态的化学反应非常有用，例如四元杂环过氧化物热解中的两个过渡态。研究了化学激发产率、解离时间和其他量对总初始动能和额外正初始速度的依赖性。通过考虑不同的CASPT2校正和额外的正初始速度，我们发现得到的三重态量子产率与实验结果完美匹配。在大多数系综中，二级初级系间窜越，即从第一单重激发态到第一三重态跃迁，是第一三重态产物轨迹的主要直接产生通道。
