Generalized Velocity Sampling at a Transition State and Nonadiabatic Dynamics of Four-Membered Heterocyclic Peroxides.

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.