Energetics, structure, and rovibrational spectroscopic properties of the sulfurous anions SNO− and OSN−

Abstract

The SNO(-) and OSN(-) anions are shown in this work to be very stable negatively charged species in line with other recent work [T. Trabelsi et al., J. Chem. Phys. 143, 164301 (2015)]. Utilizing established quartic force field techniques, the structural and rovibrational data for these anions are produced. The SNO(-) anion is less linear and has weaker bonds than the corresponding neutral radical giving much smaller rotational constants. OSN(-) is largely unchanged in these regards with inclusion of the additional electron. The S-N bond is actually stronger, and the rotational constants of OSN(-) versus OSN are similar. The vibrational frequencies of SNO(-) are red-shifted from the radical while those in OSN(-) are mixed. OSN(-) has mixing of the stretching modes while the S-N and N-S stretches of SNO(-) are largely independent of one another. The ω3 stretches are much brighter in these anions than they are in the radicals, but the ω1 stretches are still the brightest.

A Coupled Cluster Investigation of SNO Radical Isomers and Their Reactions with Hydrogen Atom: Insight into Structures, Conformers, Barriers, and Energetics

“…The structure and rovibrational features for these anions were also investigated using established quartic force field techniques. 27 The vibrational frequencies of SNO − are red-shifted from the radical, while those in NSO − are mixed. NSO − has mixing of the stretching modes, while the S−N and N−S stretches of SNO − are largely independent of one another.…”

“…Large electron affinities and a long-lived triplet state are predicted for both anions. The structure and rovibrational features for these anions were also investigated using established quartic force field techniques . The vibrational frequencies of SNO – are red-shifted from the radical, while those in NSO – are mixed.…”

On the Detectability of the HSS, HSO, and HOS Radicals in the Interstellar Medium

“…Utilizing restricted-openshell Hartree-Fock reference wavefunctions Lauderdale et al 1991;Watts et al 1993) for CCSD(T), the geometry is computed with the aug-cc-pV5Z basis set (Dunning 1989; Kendall et al 1992) with the necessary, additional tight d functions for sulfur (Wilson & Dunning 2004) as well as the Martin-Taylor (MT) core correlating basis set (Martin & Taylor 1994) inclusive and exclusive of core electrons correlated. The difference in the MT bond lengths and bond angle are added to the CCSD(T)/aug-cc-pV5Z geometry as has been done for many related systems (Fortenberry et al 2014b;Fortenberry & Francisco 2015a, 2015bFortenberry & Lukemire 2015;Fortenberry & Thackston 2015;Finney et al 2016;Kitchens & Fortenberry 2016).…”

Simplest N-Sulfonylamine HNSO2

“…Inorganic small molecules containing S, N, and O have attracted increasing interest due to the important roles in chemistry, biology, and atmosphere . For instance, radicals SNO/NSO and the corresponding anions SNO – /NSO – have been regarded as candidate species in atmospheric and astrochemistry. Moreover, the acid molecules HSNO and HNSO have been the targets of extensive experimental and theoretical studies .…”