Computed spectroscopic properties of HCN, HNC, and all their D, 13C, and 15N substituted isotopologues

Abstract

ABSTRACT Starting from ab initio electronic structure data, we develop parametrized analytic potential energy surfaces for the HCN and HNC isomers by variationally calculating rovibrational energy levels and adjusting the potential parameters so as to get agreement with experimentally derived transition frequencies to within about 1 cm−1. We also determine an analytic expression in terms of molecular parameters to effortlessly calculate the rovibrational energy levels. We use the obtained empirical potentials to calculate rovibrational levels for eight isotopologues of HCN and eight of HNC up to about 4000 cm−1 above the ground state. The energy levels are estimated to be accurate to within about 3 cm−1 based on comparison to experimental rovibrational transition frequencies for H12C14N, H12C14N, H13C14N, and H12C15N. For all 16 isotopologues, we calculate the zero-point energy and in nine cases we can compare with experimentally derived values. In these comparisons, the variationally obtained ZPE is within 5 cm−1 of the experimentally derived value, while the closed expression gives values within 6 cm−1 of the experimental values. For all 16 isotopologues, we also give molecular parameters from which the energy levels can easily be calculated using the closed expression. Endo- and exoergicities are given for 12 isotopic exchange reactions involving HCN/HNC and some isotopologues together with pre-exponential factors that should be useful in future modelling studies of rare isotopologues.