American Chemical Society
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Highly Accurate Quartic Force Field and Rovibrational Spectroscopic Constants for the Azirinyl Cation (c‑C2NH2+) and Its Isomers

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journal contribution
posted on 2020-01-03, 20:05 authored by Partha P. Bera, Xinchuan Huang, Timothy J. Lee
The azirinyl cation is an aromatic cyclic molecule that is isoelectronic with cyclopropenylidene, c-C3H2, and c-C3H3+. Cyclopropenylidene has been shown to be ubiquitous, existing in many different astrophysical environments. Given the similar chemistry between C and N, and the relative abundances between C and N in astrophysical environments, it is expected that there should be aromatic ringed molecules that incorporate N in the ring, but as yet, no such molecule has been identified. To address this issue, the present study uses high levels of electronic structure theory to compute a highly accurate quartic force field (QFF) for the azirinyl cation and its two lowest lying isomers, the cyanomethyl and isocyanomethyl cations. The theoretical approach uses the singles and doubles coupled-cluster method that includes a perturbative correction for connected triple excitations, CCSD­(T), together with extrapolation to the one-particle basis set limit and corrections for scalar relativity and core-correlation. The QFF is then used in a second-order vibrational perturbation theory analysis (VPT2) to compute the fundamental vibrational frequencies and rovibrational spectroscopic constants for all three C2NH2+ isomers. The reliability of the VPT2 vibrational frequencies is tested by comparison to vibrational configuration interaction (VCI) calculations, and excellent agreement is found between the two approaches. Fundamental vibrational frequencies and rovibrational spectroscopic constants for all singly substituted 13C, 15N, and D isotopologues are also reported. It is expected that the highly accurate spectroscopic data reported herein will be useful in the identification of these cations in high-resolution experimental or astronomical observations.