Testing the Concept of Hypervalency: Charge Density Analysis of K2SO4 (Articolo in rivista)

Type
Label
  • Testing the Concept of Hypervalency: Charge Density Analysis of K2SO4 (Articolo in rivista) (literal)
Anno
  • 2012-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1021/ic301372m (literal)
Alternative label
  • M.S. Schmøkel, S. Cenedese, J. Overgaard, M.R.V. Jørgensen, Y-S Chen, C. Gatti*, Dietmar Stalke,* and Bo B. Iversen* (2012)
    Testing the Concept of Hypervalency: Charge Density Analysis of K2SO4
    in Inorganic chemistry; ACS, American chemical society, Washington, DC (Stati Uniti d'America)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • M.S. Schmøkel, S. Cenedese, J. Overgaard, M.R.V. Jørgensen, Y-S Chen, C. Gatti*, Dietmar Stalke,* and Bo B. Iversen* (literal)
Pagina inizio
  • 8607 (literal)
Pagina fine
  • 8616 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 51 (literal)
Rivista
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#pagineTotali
  • 10 (literal)
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • 1,3-4,8: Center for Materials Crystallography, Department of Chemistry and iNANO, Aarhus University, Langelandsgade 140, DK-8000 Aarhus C., Denmark 2,6: Istituto di Scienze e Tecnologie Molecolari del CNR (CNR-ISTM) and Dipartimento di Chimica, Università di Milano, via Golgi 19, I-20133, Milano, Italy 5: ChemMatCARS, University of Chicago, Advanced Photon Source, Argonne, Illinois 60439, United States 7: Institut fuer Anorganische Chemie, Georg-August-Universitaet Goettingen, Tammannstrasse 4, 37077 Goettingen (literal)
Titolo
  • Testing the Concept of Hypervalency: Charge Density Analysis of K2SO4 (literal)
Abstract
  • One of the most basic concepts in chemical bonding theory is the octet rule, which was introduced by Lewis in 1916, but later challenged by Pauling to explain the bonding of third-row elements. In the third row, the central atom was assumed to exceed the octet by employing d orbitals in double bonding leading to hypervalency. Ever since, polyoxoanions such as SO4 2-, PO43-, and ClO4 - have been paradigmatic examples for the concept of hypervalency in which the double bonds resonate among the oxygen atoms. Here, we examine S-O bonding by investigating the charge density of the sulfate group, SO42-, within a crystalline environment based both on experimental and theoretical methods. K2SO4 is a high symmetry inorganic solid, where the crystals are strongly affected by extinction effects. Therefore, high quality, very low temperature single crystal Xray diffraction data were collected using a small crystal (~30 micrometers) and a high energy (30 keV) synchrotron beam. The experimental charge density was determined by multipole modeling, whereas a theoretical density was obtained from periodic ab initio DFT calculations. The chemical bonding was jointly analyzed within the framework of the Quantum Theory of Atoms In Molecules only using quantities derived from an experimental observable (the charge density). The combined evidence suggests a bonding situation where the S-O interactions can be characterized as highly polarized, covalent bonds, with the \"single bond\" description significantly prevailing over the \"double bond\" picture. Thus, the study rules out the hypervalent description of the sulfur atom in the sulfate group. (literal)
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