Transition-Metal-Doped Aluminum Hydrides as Building Blocks for Supramolecular Assemblies

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• 作者：Jianjun Liu ; Jiamei Yu ; Qingfeng Ge
• 刊名：Journal of Physical Chemistry A
• 出版年：2010
• 出版时间：November 25, 2010
• 年：2010
• 卷：114
• 期：46
• 页码：12318-12322
• 全文大小：149K
• 年卷期：v.114,no.46(November 25, 2010)
• ISSN：1520-5215

文摘

Density functional theory calculations were carried out to characterize a series of transition-metal-doped aluminum hydrides, forming TMAl_nH_2n and TMAl_nH_2n+1 (TM = Sc, Ti, V; n = 3,4), in either charged or neutral form. A new electron-counting rule for these clusters was formulated as PSEN (paired skeleton electron number) = 4n, which can characterize both closed-shell and open-shell clusters. On the basis of this electron-counting rule, the superatomic clusters such as TiAl₄H₉ and TiAl₃H₆ were identified and can be used to assemble supramolecular structures. Electronic structure analysis showed that three-centered TM−H−Al bonds largely contributed to the structural stability. Also, the spin state of a wide range of clusters in their ground state can be predicted by the electron-counting rule.