Nonadiabatic dynamics starting from reactant and transition state in luminol chemiluminescence

Abstract

The role of the starting configurations in nonadiabatic dynamics is investigated, and it is found for the first time that the dissociation times of the surface hopping trajectories initializing with the reactant are much greater than those starting from the transition state; however, the two sets of chemiexcitation yields are almost the same within standard errors in luminol chemiluminescence. The significant singlet chemiexcitation yield is explained by the difference between the number of S0 to S1 excitations and S1 to S0 de-excitations, and the negligible triplet can be explained similarly. The substantial singlet chemiexcitation yield obtained via the trajectory surface hopping method is attributed to the existence of the chemiexcitation region, through which the intrinsic reaction path does not pass.