Analysis of Aromaticity in Planar Metal Systems using the Linear Response Kernel.
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- 作者：Stijn Fias ; Zino Boisdenghien ; Thijs Stuyver ; Martha Audiffred ; Gabriel Merino ; Paul Geerlings ; Frank de Proft
- 刊名：The Journal of Physical Chemistry A
- 出版年：2013
- 出版时间：April 25, 2013
- 年：2013
- 卷：117
- 期：16
- 页码：3556-3560
- 全文大小：291K
- 年卷期：v.117,no.16(April 25, 2013)
- ISSN：1520-5215
文摘
The linear response kernel is used to gain insight into the aromatic behavior of the less classical metal aromatic E42鈥?/sup> and CE42鈥?/sup> (E = Al, Ga) clusters. The effect of the systematic replacement of the aluminum atoms in Al42鈥?/sup> and CAl42鈥?/sup> by germanium atoms is studied using, Al3Ge鈥?/sup>, Al2Ge2, AlGe3+, Ge42+, CAl3Ge鈥?/sup>, CAl2Ge2, CAlGe3+, and CGe42+. The results are compared with the values of the delocalization index (未1,3) and nucleus independent chemical shifts (NICSzz). Unintegrated plots of the linear response, computed for the first time on molecules, are used to analyze the delocalization in these clusters. All aromaticity indices studied, the linear response, 未1,3, and NICSzz, predict that the systems with a central carbon are less aromatic than the systems without a central carbon atom. Also, the linear response is more pronounced in the 蟽-electron density than in the 蟺-density, pointing out that the systems are mainly 蟽-aromatic.