The global potential energy surface of extrapolated to the complete basis set limit

Abstract

It has been established that the proton transfer dynamics of play an important role in determining the chain reaction of phosphorus-containing compounds in the planetary ionosphere. This work presents an accurate global potential energy surface (PES) of for the first time by fitting extensive ab initio energies from the aug-cc-pV(T, Q)Z level of theory using the multi-reference configuration interaction method including Davidson correction, and extrapolating the points to the complete basis set limit. The spectral parameters of PH+(A 2Δ) and are shown to be in agreement with the data available in previous literature. Meanwhile, a detailed study of the topographical features of the global PES could be used as a reliable photolytic kinetic theory for the reaction. Furthermore, to demonstrate the validity of the new PES, we have explicitly taken into account the reaction, and assessed its feasibility in terms of reaction dynamics by calculating the integral cross-section via the time-dependent wave packet and quasi-classical trajectory approaches. The consequent results indicate that the new PES is suitable for thermochemical reactions.