Ab initio studies of the thermochemistry of the bisulfite and the sulfonate ions and related compounds

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High-level ab initio calculations, with and without solvent effects, were completed to resolve the contradictory experimental and theoretical results on the relative stabilities of the bisulfite ion, HOSO2-, and its tautomer, the sulfonate ion, HSO3-. Calculations at the G2 level reveal that the sulfonate anion is more stable in both the gas and aqueous phases by approximately 4-5 kcal/mol. Contradictory results were obtained if inadequate polarization functions were used on the sulfur atom. The gas-phase heat of formation, ΔHf°298, for the bisulfite and sulfonate ions are respectively -165 and -169 kcal/mol. The first value compares favorably to the gas-phase experimental result equal to -165.6 ± 2.5 kcal/mol for the bisulfite anion. © 1995 American Chemical Society.

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Journal of Physical Chemistry