Department of Chemistry and Biochemistry, Southern Illinois University, Carbondale, Illinois 62901, United States.
J Phys Chem A. 2010 Nov 25;114(46):12318-22. doi: 10.1021/jp1066296. Epub 2010 Oct 29.
Density functional theory calculations were carried out to characterize a series of transition-metal-doped aluminum hydrides, forming TMAl(n)H(2n) and TMAl(n)H(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 TiAl(4)H(9) and TiAl(3)H(6) 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.
采用密度泛函理论计算方法对一系列过渡金属掺杂的氢化铝（TMAl(n)H(2n)和 TMAl(n)H(2n+1)，TM = Sc、Ti、V；n = 3、4）进行了结构特征分析，其中 TMAl(n)H(2n)和 TMAl(n)H(2n+1)可以以带电或中性形式存在。为这些团簇制定了一个新的电子计数规则 PSEN（配对骨架电子数）= 4n，该规则可用于表征闭壳层和开壳层团簇。在此电子计数规则的基础上，鉴定了 TiAl(4)H(9)和 TiAl(3)H(6)等超原子团簇，这些团簇可用于组装超分子结构。电子结构分析表明，三中心 TM-H-Al 键对结构稳定性有很大贡献。此外，还可以通过电子计数规则预测大多数团簇基态的自旋态。
