ABSTRACT:Bonding in the hypervalent molecules SF , BrF , PF , and SF was belonging to type II. The eigenvalues and eigenvectors of type I molecules distinguished between classic two-center two-electron bonds and three-center four-electron bonds, whereas the results of diagonalization for type II molecules demonstrated the presence of substantial reorganization of the valence state of the central atom leading to equivalent bonds and the highest expected symmetry of the molecule. ᮊ

Bonding in the hypervalent molecules SF4, BrF5, PF5, and SF6 was studied using multicenter bond order indices and examination of the eigenvalues and the eigenvectors of the Fermi holes of the constituent atoms. Diagonalization of the Fermi holes provided quantitative validation of Musher's categorization of hypervalency with SF4 and BrF5 representative of type I, and PF5 and SF6 belonging to type II. The eigenvalues and eigenvectors of type I molecules distinguished between classic two‐center two‐electron bonds and three‐center four‐electron bonds, whereas the results of diagonalization for type II molecules demonstrated the presence of substantial reorganization of the valence state of the central atom leading to equivalent bonds and the highest expected symmetry of the molecule. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 760–771, 1999

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Effects of correlation on one-electron distribution and other properties are calculated for the H3+ molecule ion. Effects due to singly substituted and doubly substituted configurations are essentially additive for this closed shell species. The effect of doubly substituted configurations is to shift charge from the molecular center to nuclear regions, mainly outside the molecule. This is rationalized in terms of the many-electron theory of Sinanoğlu. The singly substituted configurations cause a slight electronic contraction similar to that caused by initial atomic—molecular formation. Neglect of singly substituted configurations is not justified when one is seeking improvement of properties beyond the HF-SCF level.