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Ab initio MO calculations for the oxides, oxyacids, and oxyanions of S( IV ) and S( VI )
Author(s) -
Baird N. Colin,
Taylor Kathleen F.
Publication year - 1981
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540020303
Subject(s) - chemistry , ab initio , hypervalent molecule , basis set , deprotonation , atomic orbital , sulfur , crystallography , molecular orbital , bond length , ab initio quantum chemistry methods , computational chemistry , molecule , density functional theory , physics , crystal structure , ion , organic chemistry , quantum mechanics , reagent , electron
Ab initio molecular orbital ( MO ) calculations for two series of sulfur–oxygen compounds are reported: the S( IV ) system of SO 2 , H 2 SO 3 , HSO 3 − , and SO 3 2− , and the S( VI ) system of SO 3 , H 2 SO 4 , HSO 4 − , and SO 4 2− . Geometries about the sulfur atoms were optimized using the STO ‐3G* basis set; energies at these geometries were computed by the STO −3G and 44‐31G basis sets both with and without five Gaussian d orbitals on S. The sulfur–oxygen bond lengths and the angles about the central atoms agree fairly well with experiment. The stabilization energy associated with the addition of the d orbitals was found to be a constant amount per bond (ca. 54 and 28 kcal mole −1 in the minimal and extended bases, respectively) in hypervalent compounds. The isomer HSO 3 −was predicted to be more stable than SO 2 (OH) − , but the reverse was true for HSO 2 (OH) compared to SO(OH) 2 . The deprotonation energies for the acids and the hydration energies for the oxides also were computed and discussed with reference to experimental data.