Rotational Spectrum of the β-Cyanovinyl Radical: A Possible Astrophysical N-Heterocycle Precursor

A fundamental question in the field of astrochemistry is whether the molecules essential to life originated in the interstellar medium (ISM), and, if so, how they were formed. Nitrogen-containing heterocycles are of particular interest because of their role in biology; however, to date, no N-heterocycle has been detected in the ISM, and it is unclear how and where such species might form. Recently, the β-cyanovinyl radical (HCCHCN) was implicated in the low-temperature gas-phase formation of pyridine. While neutral vinyl cyanide (H 2 CCHCN) has been rotationally characterized and detected in the ISM, HCCHCN has not. Here, we present the first theoretical study of all three cyanovinyl isomers at the CCSD(T)/ANO1 level of theory and the experimental rotational spectra of cis- and trans-HCCHCN, as well as those of their 15 N isotopologues, from 5 to 75 GHz. The observed spectra are in good agreement with calculations and provide a basis for further laboratory and astronomical investigations of these radicals.