Theoretical study of the dissociation reaction HFCO→HF+CO: New ab initio potential function and classical trajectory analysis

Abstract

A total of 3261 ab initio energies calculated at the RHF/MP2 level were used to obtain an analytical representation of the potential energy surface (PES) for the title reaction considering all the vibrational degrees of freedom. The analytical potential is constructed by switching three local representations of the PES utilizing a distancelike function, and it reproduces well the ab initio energies up to 20 kcal/mol above the dissociation threshold with the root-mean-square (rms) deviation equal to 1.5 kcal/mol. Two types of classical trajectory studies, i.e., power spectra calculations and product-state distribution analysis, were performed to assess the reliability of the present potential function. The results were found to be in good agreement with the available experimental ones.