An observable-based interpretation of electronic wavefunctions

application to "hypervalent" molecules

Jerzy Cioslowski, P. Surján

Research output: Contribution to journalArticle

137 Citations (Scopus)

Abstract

The quantum-mechanical definition of observables is extended to all properties that can be derived from experimentally measurable quantities with the help of universal operators. Even such an extended definition, however, does not cover several commonly used concepts such as atomic orbitais in molecules or Mulliken atomic charges. Principles of an observable-based interpretation of electronic wavefunctions are outlined. Such an approach avoids ill-defined properties and concepts, therefore minimizing arbitrariness inherent in the interpretation process. Currently known atomic and bond quantities that are observable are reviewed and applied to four "hypervalent" molecules containing sulfur atoms. It is found that the S-O bonds in the molecules under study have highly ionic character and bond orders close to unity. This clear-cut analysis demonstrates that the octet rule is not violated in "hypervalent" compounds with one or two S-O bonds.

Original languageEnglish
Pages (from-to)9-33
Number of pages25
JournalJournal of Molecular Structure: THEOCHEM
Volume255
Issue numberC
DOIs
Publication statusPublished - Mar 24 1992

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Wave functions
Sulfur
Molecules
electronics
molecules
octets
unity
sulfur
operators
Atoms
atoms

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computational Theory and Mathematics
  • Atomic and Molecular Physics, and Optics

Cite this

An observable-based interpretation of electronic wavefunctions : application to "hypervalent" molecules. / Cioslowski, Jerzy; Surján, P.

In: Journal of Molecular Structure: THEOCHEM, Vol. 255, No. C, 24.03.1992, p. 9-33.

Research output: Contribution to journalArticle

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