A theoretical study of models for X sub 2 Y sub 2 zintl ions

Journal Article · Wed Oct 11 00:00:00 EDT 1989 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00203a006· OSTI ID:6664861

Cave, R J; Davidson, E R ^[1]; Sautet, P; Canadell, E; Eisenstein, O ^[2]

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1. Indiana Univ., Bloomington (USA)
2. Laboratoire de Chimie Theorique, Orsay (France)

Ab initio and extended Hueckel calculations have been used to discuss the bonding scheme in X{sub 2}Y{sub 2} neutral and ionic main group clusters. A qualitative analysis suggests that two different electron counts, 20 and 22, are possible for the butterfly structures of these systems. This results from two orbital crossings in the correlation diagram for the tetrahedral (T{sub d}) {yields} butterfly (C{sub 2{nu}}) {yields} square-planar (D{sub 2h}) transformation. Detailed ab initio computations substantiate this analysis and show that the 20-electron butterfly structure becomes increasingly favored over the tetrahedral one in X{sub 2}Y{sub 2} clusters when the 2 atoms have increasing electronegativity difference. These results are in agreement with the known structures for the Pb{sub 2}Sb{sub 2}{sup 2{minus}} and Sb{sub 2}Bi{sub 2}{sup 2{minus}} clusters (tetrahedral-like) and the Tl{sub 2}Te{sub 2}{sup 2{minus}} one (butterfly-like).

• OSTI ID: 6664861
• Journal Information: Journal of the American Chemical Society; (USA), Vol. 111:21; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
99 GENERAL AND MISCELLANEOUS//MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE
36 MATERIALS SCIENCE
ANTIMONY COMPLEXES
CLUSTER MODEL
LEAD COMPLEXES
MOLECULES
THALLIUM TELLURIDES
CALCULATION METHODS
DATA ANALYSIS
MATHEMATICAL MODELS
THEORETICAL DATA
CHALCOGENIDES
COMPLEXES
DATA
INFORMATION
NUCLEAR MODELS
NUMERICAL DATA
TELLURIDES
TELLURIUM COMPOUNDS
THALLIUM COMPOUNDS
400200* - Inorganic
Organic
& Physical Chemistry
990200 - Mathematics & Computers
360102 - Metals & Alloys- Structure & Phase Studies