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Valence bonds in the main group elements. 2. The sulfur oxides

Journal Article · · Journal of the American Chemical Society; (USA)
DOI:https://doi.org/10.1021/ja00167a007· OSTI ID:6880066
 [1];  [2]
  1. Univ. of Pennsylvania, Philadelphia (USA)
  2. General Electric Corporate Research and Development, Schenectady, NY (USA)
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.
OSTI ID:
6880066
Journal Information:
Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:11; ISSN 0002-7863; ISSN JACSA
Country of Publication:
United States
Language:
English