TY - JOUR A1 - Drozdova, Y. A1 - Steudel, R. A1 - Hertwig, R. H. A1 - Koch, W. A1 - Steiger, Thomas T1 - Structures and Energies of Various Isomers of Dithionous Acid H2S2O4 and of Its Anion HS2O4 JF - The journal of physical chemistry / A N2 - Ab initio molecular orbital calculations at various, correlated levels of theory have been performed on eight isomers of the [H,O4,S2]- anion and six forms of [H2,O4,S2]. For the former species, the hypothetical O3SSOH- (9) ion is identified as the lowest energy isomer using second-order Mller-Plesset perturbation theory or the CCSD(T) method, with the protonated dithionite ion, O2SSO2H- (6), being only marginally (less than 5 kJ mol-1 at 25 C) higher in energy. In contrast, the B3LYP density functional predicts a rather different order of relative stabilities, with O2SSO2H- (6) as the by far most stable ion. 6 is stable with respect to dissociation into SO2 and HOSO- or into SO2- and HOSO (which is more stable than HSO2). For the species of composition H2S2O4 the cagelike dithionous acid molecule (HO)O2SSO2(OH) (14) represents the global minimum at all four levels of theory. However, also for this species, the relative stabilities predicted by the B3LYP approach differ considerably from results obtained from the conventional wave function-based methods. 14 is stabilized by two very strong intramolecular hydrogen bonds (symmetry C2). The homolytic dissociation of 14 at the SS bond is strongly endothermic, but the molecule is unstable with respect to dissociation into H2SO2 and SO2. The harmonic wavenumbers and infrared intensities of the fundamental vibrations of 6 and 14 are given. PY - 1998 DO - https://doi.org/10.1021/jp972658d SN - 1089-5639 SN - 1520-5215 VL - 102 IS - 6 SP - 990 EP - 996 PB - Soc. CY - Washington, DC AN - OPUS4-2587 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Steudel, R. A1 - Steiger, Thomas T1 - Sulfur compounds. Part 162. Geometries and energies of the radical anion SO2- and of three isometric structures of the dithionite anion S2O4 2- alpha JF - Journal of molecular structure PY - 1993 SN - 0022-2860 SN - 1872-8014 SN - 0377-046X VL - 284 SP - 55 EP - 59 PB - Elsevier CY - Amsterdam AN - OPUS4-2678 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Steiger, Thomas A1 - Steudel, R. T1 - Sulphur compounds. Part 149. Structures, relative stabilities and vibrational spectra of several isomeric forms of sulphoxylic acid (H2SO2) and its anion (HSO2-): an ab initio study alpha JF - Journal of molecular structure PY - 1992 SN - 0022-2860 SN - 1872-8014 SN - 0377-046X SP - 313 EP - 323 PB - Elsevier CY - Amsterdam AN - OPUS4-4583 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -