Spectroscopic Properties of Polysulfide Anions, Radical Anions, and Molecules: Ab Initio Calculations and Application to Minerals of the Sodalite and Cancrinite Groups

Until 2021, experimental data on polysulfide groups in feldspathoids were limited to the properties of the S₃^·− chromophore center and the S₂^·− luminescence center in sodalite-group minerals. Interpretation of some spectroscopic data on other S-bearing groups in feldspathoids remained ambiguous because of significant differences between calculated data for isolated polysulfide species and experimental data for polysulfide groups in liquid sulfur, solutions, and matrix-isolated species published in different literature sources. For this reason, configurations of stable and metastable structures and parameters of the absorption spectra in the ultraviolet, visible, and near-infrared (UV-Vis-NIR) region and in the ESR and Raman spectra of various structure modifications of polysulfide S_n²⁻ anions, S_n^·− radical anions, and S_n neutral molecules (n = 2–6) as well as HS⁻ in the sodalite cage of sapozhnikovite have been calculated in frames of the density functional theory using the VASP and ORCA software packages. Taking into account the obtained results of theoretical calculations, spectroscopic properties of extra-framework polysulfide groups in natural tectosilicates belonging to the cancrinite and sodalite groups are discussed. The obtained results made it possible to confirm and partially clarify the interpretation of the experimental spectroscopic data for S-containing feldspathoids obtained by the authors of this work over the past five years.