Nonadiabatic dynamics studies of the P + ( 3 P) + H 2 reaction using time-dependent wave packet method

Abstract

Abstract

Abstract The adiabatic and nonadiabatic dynamics of the P + ( 3 P) + H 2  PH + (X 2 ) + H reaction are investigated using the time-dependent wave packet method in the collision energy range of 1.0-3.0 eV. The reaction probabilities, integral cross sections, differential cross sections, the rovibrational state distribution of product, and rate constants are calculated and compared between the adiabatic and nonadiabatic treatments. The results show that adiabatic results always overestimated the actual value. The nonadiabatic effect plays an important role in the reaction, manifesting not only as changes in magnitude but also as significant influences on the rovibrational state distributions of the product, especially for the ground and first excited vibrational states. The differential cross sections exhibit forward-backward symmetry when the collision energies below 2.0 eV, indicating a dominant insertion mechanism via a long-lived complex formed in the deep well. As the collision energy further increases, the reaction mechanism begins to transition from an insertion mechanism to an abstraction mechanism.