Valence bonds in the Main Group elements. 2. The sulfur oxides

A new bonding description is presented for SO{sub 2}, S{sub 2}O, S{sub 3}, SO{sub 3}, H{sub 2}SO{sub 4}, and SO{sub 4}{sup 2{minus}}, based on a single valence bond (VB) structure in each case. The results are derived from generalized valence bond (GVB) calculations, which provide accurate predictio...

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Bibliographic Details
Published in:Journal of the American Chemical Society 1990-05, Vol.112 (11), p.4138-4150
Main Authors: Patterson, Charles H, Messmer, Richard P
Format: Article
Language:English
Subjects:
BONDING
CALCULATION METHODS
CHALCOGENIDES
ELECTRONIC STRUCTURE
FABRICATION
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
JOINING
MATHEMATICAL MODELS
NUCLEAR MODELS
OXIDES
OXYGEN COMPOUNDS
SULFUR COMPOUNDS 400201 > Chemical & Physicochemical Properties
SULFUR DIOXIDE
SULFUR OXIDES
VALENCY MODEL
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Summary:A new bonding description is presented for SO{sub 2}, S{sub 2}O, S{sub 3}, SO{sub 3}, H{sub 2}SO{sub 4}, and SO{sub 4}{sup 2{minus}}, based on a single valence bond (VB) structure in each case. The results are derived from generalized valence bond (GVB) calculations, which provide accurate predictions of the experimental geometries, and contrast with the usual valence bond models for these species, which require more than one VB structure (i.e., resonance). The molecules SO{sub 2}, S{sub 2}O, and S{sub 3} possess sulfur lone pairs that are angularly correlated. This angular separation of the two electrons within a long pair occurs when charge is removed from the sulfur atom by electronegative atoms. Such a separation of lone pair electrons allows for the formation of additional bonds beyond that permitted by the Octet Rule. The role of d functions in the electronic structure of molecules containing second-row atoms is also considered. All calculations were performed within the GVB-PP method, i.e. incorporating the strong orthogonality and perfect pairing (SOPP) approximations.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja00167a007