期刊
JOURNAL OF COMPUTATIONAL CHEMISTRY
卷 30, 期 16, 页码 2764-2776出版社
WILEY
DOI: 10.1002/jcc.21291
关键词
3c-2e bonding; alkaline earth metal clusters; sigma-aromaticity; pi-aromaticity; aromaticity tuning; DFT calculations
资金
- Spanish MEC [CTQ2008-03077/BQU]
- Catalan Departament d'Universitats, Recerca i Societat de la Informacio (DURSI) [2005SGR-00238]
- Generalitat de Catalunya
- Social European Fund [2005FI/00451]
In this work, we analyze the geometry and electronic structure of the [XnM3](n-2) species (M = Be, Mg, and Ca; X = Li, Na, and K; n = 0, 1, and 2), with special emphasis on the electron delocalization properties and aromaticity of the cyclo-[M-3](2-) unit. The cyclo-[M-3](2-) ring is held together through a three-center two-electron bond of sigma-character. Interestingly, the interaction of these small clusters with alkali metals stabilizes the cyclo-[M-3](2-) ring and leads to a change from sigma-aromaticity in the bound state of the cyclo-[M-3](2-) to pi-aromaticity in the XM3- and X2M3 metallic clusters. Our results also show that the aromaticity of the cyclo-[M-3](2-) unit in the X2M3 metallic clusters depends on the nature of X and M. Moreover. we explored the possibility for tuning the aromaticity by simply moving X perpendicularly to the center of the M-3 ring. The Na2Mg3, Li2Mg3, and X2Ca3 clusters undergo drastic aromaticity alterations when changing the distance from X to the center of the M-3 ring, whereas X2Be3 and K2Mg3 keep its aromaticity relatively constant along this process. (C) 2009 Wiley Periodicals, Inc. J Comput Chem 30: 2764-2776, 2009
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