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Theoretical determination of lowest structures of all‐metal aromatic clusters M 4 L 2 (M = Al, Ga, In, Tl; L = Li, Na, K, Rb, Cs)
Author(s) -
Mang Chaoyong,
Liu Caiping,
Wu Kechen
Publication year - 2010
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.22108
Subject(s) - chemistry , cluster (spacecraft) , aromaticity , laser vaporization , metal , alkali metal , crystallography , coupled cluster , quantum chemical , atomic physics , computational chemistry , laser , physics , molecule , organic chemistry , computer science , optics , programming language
Abstract The researches of all‐metal aromatic clusters have been a thermic theme in inorganic aromaticity domain both experimentally and theoretically since the Al 4 L − (L = Li, Na, Cu) clusters were created by laser vaporization. In systemic determination of the lowest structures of 20 gaseous all‐metal aromatic clusters M 4 L 2 (M = Al, Ga, In, Tl; L = Li, Na, K, Rb, Cs), the isomer energy differences of four low‐lying structures of each cluster were evaluated at high‐quality quantum chemistry levels. Single point calculations at the coupled cluster level were performed at geometries optimized at the MP2, B3LYP, and B3PW91 levels, and harmonic frequency calculations and zero point energy corrections were implemented following optimizations at the B3LYP and B3PW91 levels. In addition to Li‐ and Na‐containing species, theoretical investigations came down to those new clusters including K, Rb, and Cs. For many clusters, the most convincing theoretical evidences indicate that the lowest structures are a square bipyramidal isomer rather than an edge‐caped square pyramidal species. A few discrepancies were addressed at the MP2, B3LYP, and B3PW91 levels in comparison with the coupled cluster results. These findings are significant because some clusters were generated by laser vaporization and served as theoretical prototypes to test the new means for assessing aromaticity. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010