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Electronegativity equalization and the electronic structure of polyhedral clusters of main‐group atoms
Author(s) -
Lohr Lawrence L.
Publication year - 1984
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560250117
Subject(s) - electronegativity , formal charge , group (periodic table) , charge (physics) , chemistry , main group element , molecule , atomic charge , atomic physics , crystallography , electronic structure , computational chemistry , chemical physics , molecular physics , physics , transition metal , quantum mechanics , catalysis , biochemistry , organic chemistry
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 Sn 9−x Pb x 4− (x = 0 → 9), Sn 9‐x Ge x 4− , Sn 8−x Pb x Tl 5− , Sn 2 Bi 2 2− , SnTe 4 4− , etc. The role of the relativistic spin‐orbit splitting of an np shell into np 1/2 and np 3/2 subshells in modifying atomic and hence molecular electronegativities is discussed. Correlations are made between calculated charge distributions and observed 199 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.