Electronic and geometric stabilities of clusters with transition metal encapsulated by silicon
Electronic and geometric stabilities of clusters with transition metal encapsulated by silicon
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DOI：
10.1021/jp066757f
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发表时间：
2007-01-11
影响因子：
2.9
通讯作者：
Nakajima, Atsushi
中科院分区：
文献类型：
--
作者：
Koyasu, Kiichirou;Atobe, Junko;Nakajima, Atsushi
采用双激光蒸发法制备了掺杂过渡金属原子MSin的硅团簇，并对硅包裹过渡金属团簇的电子稳定性和几何稳定性进行了实验研究.通过系统的掺杂与过渡金属原子的第3，4，和5组（M = Sc，Y，Lu，Ti，Zr，Hf，V，Nb，和Ta），然后通过改变电荷状态，我们探索了使用的电子关闭的硅笼状集群和变化，其腔的大小，以促进金属原子的封装。通过质谱，阴离子光电子能谱，和对H2O的吸附反应性得到的结果表明，掺杂有第4族原子的中性簇具有电子和几何闭合n = 16。具有第4族原子的MSi 16团簇在（i）金属原子被具有第3族或第5族原子的相邻金属取代时的价电子数和（ii）原子半径被Zr和Hf的相同族元素取代时经历电子变化。卤素原子与MSi 16团簇的反应性表明，VSi 16 F形成了具有离子键的超原子络合物。
Silicon clusters mixed with a transition metal atom, MSin, were generated by a double-laser vaporization method, and the electronic and geometric stabilities for the resulting clusters with transition metal encapsulated by silicon were examined experimentally. By means of a systematic doping with transition metal atoms of groups 3, 4, and 5 (M = Sc, Y, Lu, Ti, Zr, Hf, V, Nb, and Ta), followed by changes of charge states, we explored the use of an electronic closing of a silicon caged cluster and variations in its cavity size to facilitate metal-atom encapsulation. Results obtained by mass spectrometry, anion photoelectron spectroscopy, and adsorption reactivity toward H2O show that the neutral cluster doped with a group 4 atom features an electronic and a geometric closing at n = 16. The MSi16 cluster with a group 4 atom undergoes an electronic change in (i) the number of valence electrons when the metal atom is substituted by the neighboring metals with a group 3 or 5 atom and in (ii) atomic radii with the substitution of the same group elements of Zr and Hf. The reactivity of a halogen atom with the MSi16 clusters reveals that VSi16F forms a superatom complex with ionic bonding.