Theoretical studies of sulfurous species of importance in atmospheric chemistry. 1. Characterization of the HSO and SOH isomers

The molecular structures, relative energies, and vibrational frequencies of the two stable isomers formed by the addition of H([sup 2]) to SO(X[sup 3][Sigma][sup [minus]]), namely, HSO and SOH, are computed using multiconfiguration wave functions and correlation-consistent basis sets of up to quintu...

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Bibliographic Details
Published in:Journal of physical chemistry (1952) 1993-06, Vol.97:25
Main Authors: Xantheas, S.S., Dunning, T.H. Jr
Format: Article
Language:English
Subjects:
400201 - Chemical & Physicochemical Properties
540110
ATMOSPHERIC CHEMISTRY
CATALYSIS
CHEMICAL REACTIONS
CHEMISTRY
DATA
ENVIRONMENTAL SCIENCES
INFORMATION
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
ISOMERIZATION
ISOMERS
MATHEMATICAL MODELS
MOLECULAR STRUCTURE
NUMERICAL DATA
OZONE
SULFUR COMPOUNDS
THEORETICAL DATA
THERMODYNAMICS
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Summary:The molecular structures, relative energies, and vibrational frequencies of the two stable isomers formed by the addition of H([sup 2]) to SO(X[sup 3][Sigma][sup [minus]]), namely, HSO and SOH, are computed using multiconfiguration wave functions and correlation-consistent basis sets of up to quintuple [zeta] quality. Contrary to results from previous calculations, the HSO isomer is predicted to be more stable than the SOH isomer by 5.4 kcal/mol. The barrier for the migration of the H atom between the two isomers is computed to be 46.3 kcal/mol. The transition state for the isomerization of the two species lies below the dissociation limit to H([sup 2]S) and SO(X[sup 3][Sigma][sup [minus]]), which is calculated to be 56.2 kcal/mol above the HSO minimum. The minimum energy paths corresponding to the addition of H([sup 2]S) to SO(X[sup 3][Sigma][sup [minus]]) to form HSO and SOH are also computed; a barrier of 2.4 kcal/mol is predicted for the addition of hydrogen to the oxygen side of SO. Finally, upper limits for [Delta]H[sub f][degrees][sub 298] for HSO and SOH are estimated at [minus]6.1 [+-] 1.3 and [minus]0.7 [+-] 1.3 kcal/mol, respectively. The latter implies that HSO can be involved in a catalytic cycle that depletes ozone in the atmosphere. 32 refs., 11 figs., 11 tabs.
ISSN:0022-3654
1541-5740
DOI:10.1021/j100127a010