Simulating UV-VIS Spectra for Polysulfur Species in the Venusian Atmosphere

The Venusian atmosphere has everything to be an exciting natural sulfur laboratory. In addition to relatively high concentrations of sulfur dioxide, suitable conditions in the atmosphere make both thermo- and photochemical reactions possible, allowing for complex chemical reactions and the formation of new sulfur containing compounds. These compounds could explain or contribute to the enigmatic 320-400 nm absorption feature in the atmosphere. One of the proposed absorbers is polysulfur compounds. While some experimentally obtained UV-VIS spectra have been published, studying the different polysulfur species individually is extremely difficult due to the reactive nature of sulfur. In this work UV-VIS spectra for polysulfur species S2 to S8 were simulated using the nuclear ensemble approach to determine if they fit the absorption profile of the unknown absorber.Geometries were optimized at the ωB97X-D/aug-cc-pV(T+d)Z level of theory, with the S2, S3, and S4 structures also being optimized at the CCSD(T)/aug-cc-pV(T+d)Z level of theory. For the lowest energy isomers UV-VIS spectra were simulated using a nuclear ensemble of 2000 geometries, with vertical excitations calculated at the EOM-CCSD/def2-TZVPD or the ωB97X-D/def2-TZVPD levels of theory.The simulated UV-VIS spectra for the smaller species were in quite good agreement with experimental results. Two different molecules were identified with substantial absorption cross sections in the range of the unknown absorber: The open chain isomer of S3, and the trigonal isomer of S4 However, the mixing ratios of these species in the Venusian atmosphere are also needed to make a more conclusive statement. Other polysulfur compounds have insignificant absorption cross sections in the 320-400 nm range and can therefore be excluded.The calculated absorption cross sections can be used to calculate photolysis rates, which can be straight away added to atmospheric models of Venus. In addition, this work will help future space missions to Venus, for example by focusing their search for the unknown absorber.