Global Diabatic Potential Energy Surfaces for the BH 2 and Dynamics Studies for the B( 2p 2 P ) + H 2 Reaction

ABSTRACT The global diabatic potential energy surfaces (PESs) of the BH 2 system were constructed using neural network method in conjunction with a specific function based on 11 553 ab initio points. We have carefully examined the diagonal elements V 11 , V 22 and the off‐diagonal element V 12 of the diabatic PESs matrix and compared them with the ab initio points. The theoretical results show that the diagonal elements V 11 and V 22 can reasonably describe the non‐adiabatic processes between the electronic states. The shape of the off‐diagonal element V 12 is regular and can satisfy the group symmetry operations. To clarify the influence of non‐adiabatic effects in B(2p 2 P) + H 2 reaction, both adiabatic and non‐adiabatic dynamics calculations were performed based on the newly constructed diabatic PESs. In addition, the adiabatic dynamical results are compared with the non‐adiabatic ones. The results show that the non‐adiabatic effects play an important role in the reaction process, while the adiabatic dynamical results are not reliable.