Volume 25, Issue 1 pp. 211-221
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Electronegativity equalization and the electronic structure of polyhedral clusters of main-group atoms

Lawrence L. Lohr Jr.

Lawrence L. Lohr Jr.

Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, U.S.A.

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First published: January 1984
Citations: 6

Abstract

The concept of the equalization of atomic electronegativities accompanving molecule formation is applied to a study of the electronic structure of polyhedral clusters of main-group atoms such as Ge, Sn, Pb, Tl, and Bi. Emphasis is placed upon charged clusters such as Sn9−x Pburn:x-wiley:00207608:media:QUA560250117:tex2gif-stack-1(x = 0 → 9), Sn9-xGeurn:x-wiley:00207608:media:QUA560250117:tex2gif-stack-2, Sn8−xPbx Tl5−, Sn2Biurn:x-wiley:00207608:media:QUA560250117:tex2gif-stack-3, SnTeurn:x-wiley:00207608:media:QUA560250117:tex2gif-stack-4, etc. The role of the relativistic spin-orbit splitting of an np shell into np1/2 and np3/2 subshells in modifying atomic and hence molecular electronegativities is discussed. Correlations are made between calculated charge distributions and observed199 Sn NMR chemical shifts for clusters of a given size and charge. It is concluded that a useful picture of charge distributions in these clusters may be obtained from electronegativity equalization considerations.

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