The stable isomers and electronic states of [S,S,N,O] species are investigated with a special focus on the most relevant isomers that could be involved in the NO/HS cross-talk pathways in biological media. This work identifies eight stable anions, among which are the already known cis-SSNO and trans-SSNO molecules and a new NO-like anionic species, NSO. Our computations show that the previously determined structure in lab experiment is trans-SSNO, which is not relevant for biological activity in vivo. Instead, NSO is proposed as the most likely key intermediate in vivo during important biological processes. This result alleviates the corresponding controversy in the literature.

We use accurate ab initio methodologies at the coupled cluster level ((R)­CCSD­(T)) and its explicitly correlated version ((R)­CCSD­(T)-F12) to investigate the electronic structure, relative stability, and spectroscopy of the stable isomers of the [S2O2] system and of some of its cations and dications, with a special focus on the most relevant isomers that could be involved in terrestrial and planetary atmospheres. This work identifies several stable isomers (10 neutral, 8 cationic, and 5 dicationic), including trigonal-OSSO, cis-OSSO, and cyc-OSSO. For all these isomers, we calculated geometric parameters, fragmentation energies, and simple and double ionization energies of the neutral species. Several structures are identified for the first time, especially for the ionic species. Computations show that in addition to cis-OSSO and trans-OSSO proposed for the absorption in the near-UV spectrum of the Venusian atmosphere other S2O2, S2O2 +, and S2O2 2+ species may contribute. Moreover, the characterization of the stability of singly and doubly charged S2O2 entities can also be used for their identification by mass spectrometry and UV spectroscopy in the laboratory or in planetary atmospheres. In sum, the quest for the main UV absorber in Venus’ atmosphere is not over, since the physical chemistry of sulfur oxides in Venus’ atmosphere is far from being understood.