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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 (H2CCHCN) 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 15N 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.

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 (H2CCHCN) 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 15N 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.

Thionitrous acid (HSNO), a potential key intermediate in biological signaling pathways, has been proposed to link NO and H2S biochemistries, but its existence and stability in vivo remain controversial. We establish that HSNO is spontaneously formed in high concentration when NO and H2S gases are mixed at room temperature in the presence of metallic surfaces. Our measurements reveal that HSNO is formed by the reaction H2S + N2O3 → HSNO + HNO2, where N2O3 is a product of NO disproportionation. These studies also suggest that further reaction of HSNO with H2S may form HNO and HSSH. The length of the S-N bond has been derived to high precision and is found to be unusually long: 1.84 Å, the longest S-N bond reported to date for an R-SNO compound. The present structural and, particularly, reactivity investigations of this elusive molecule provide a firm foundation to better understand its potential physiological chemistry and propensity to undergo S-N bond cleavage in vivo.

Thionitrous acid (HSNO), a potential key intermediate in biological signaling pathways, has been proposed to link NO and H2S biochemistries, but its existence and stability in vivo remain controversial. We establish that HSNO is spontaneously formed in high concentration when NO and H2S gases are mixed at room temperature in the presence of metallic surfaces. Our measurements reveal that HSNO is formed by the reaction H2S + N2O3 → HSNO + HNO2, where N2O3 is a product of NO disproportionation. These studies also suggest that further reaction of HSNO with H2S may form HNO and HSSH. The length of the S-N bond has been derived to high precision and is found to be unusually long: 1.84 Å, the longest S-N bond reported to date for an R-SNO compound. The present structural and, particularly, reactivity investigations of this elusive molecule provide a firm foundation to better understand its potential physiological chemistry and propensity to undergo S-N bond cleavage in vivo.