Molecular modeling annual

, Volume 6, Issue 2, pp 282–288

How relevant are S=O and P=O Double Bonds for the Description of the Acid Molecules H2SO3, H2SO4, and H3PO4, respectively?

  • Thorsten Stefan
  • Rudolf Janoschek

DOI: 10.1007/PL00010730

Cite this article as:
Stefan, T. & Janoschek, R. J Mol Model (2000) 6: 282. doi:10.1007/PL00010730


The acid molecules H2SO3, H2SO4, and H3PO4 are usually drawn using "Lewis structures" which exhibit the octet extension by 3d-orbitals on sulfur and phosphorus, respectively. Thus, S=O and P=O double bonds are assumed to be formed. The natural d-orbital occupancies on S and P, however, were calculated to be as low as 0.1 e, and therefore, an octet extension can hardly be expected. After the natural bond orbitals (NBO) search procedure was forced to attempt to form different Lewis structures of bonds and lone pairs, we defined the optimal Lewis structure, if a dominant structure exists at all, by the maximum electronic charge in Lewis orbitals. Indeed, sulfur obeys the octet rule in the optimal zwitterionic Lewis structures and does not form S=O double bonds. No dominant resonance structure could be found for H3PO4 where polarized PO π-bond and zwitterionic PO bond structures exhibit similar weights.

Keywords:Acid molecules, Lewis structures, Natural bond orbitals, Octet rule 

Copyright information

© Springer-Verlag Berlin Heidelberg 2000

Authors and Affiliations

  • Thorsten Stefan
    • 1
  • Rudolf Janoschek
    • 1
  1. 1.Institut für Theoretische Chemie, Karl-Franzens-Universität Graz, Strassoldogasse 10, A-8010 Graz, Austria. Tel.: +43- 316-380-8865; Fax: +43-316-380-9893. E-mail:

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