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Features of electronic structure of hypovalent lithides ALi/sub k/ and ALi/sub k+1//sup +/

Journal Article · · J. Struct. Chem. (Engl. Transl.); (United States)
OSTI ID:5807217

The features of the chemical bonding and the behavior of the original energies of the lithides ALi/sub k/ and ALi/sub K+1//sup +/ have been analyzed on the basis of nonempirical calculations in the MP3/(DZHD + P/sub A/) approximation. It has been found that the new A-Li bond appearing upon the addition of Li/sup +/ to Ali/sub k/ is formed with the participation of only the p/sub A/ AO's from the atom A. In contrast to the case of the hydrides AK/sub k/ and the fluorides AF/sub k/, in the case of the lithides ALi/sub k/ and ALi/sub k+1//sup +/, the lone pair of the atom A consists of its almost pure s/sub A/ AO, which maintains its spherical shape, is not active stereochemically, and practically does not participate in the bonding. The lithides ALi/sub k/ and Ali/sub k+1//sup +/ (such as CLi/sub 2/, Cli/sub 3//sup +/, NLi/sub 3/, NLi/sub 4//sup +/, OLi/sub 2/, OLi/sub 3//sup +/, Fli, Fli/sub 2//sup +/, etc.) may be classified as hypovalent compounds, in which the number of valence AO's of the atom A participating in the bonding is smaller than the number of atoms of Li directly bonded to the atom A. The bonding in them is delocalized over all the atoms comparing the molecule, and the two-center approach and Gillespie's rules are, in principle, not suitable.

OSTI ID:
5807217
Journal Information:
J. Struct. Chem. (Engl. Transl.); (United States), Journal Name: J. Struct. Chem. (Engl. Transl.); (United States) Vol. 29:3; ISSN JSTCA
Country of Publication:
United States
Language:
English

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