Department of Advanced Material Science, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8561, Japan.
J Chem Phys. 2010 Aug 21;133(7):074305. doi: 10.1063/1.3474996.
We present the formation of hydrogen-content-controlled B(12)H(n) (+) clusters through the decomposition and ion-molecule reactions of the decaborane (B(10)H(14)) and diborane (B(2)H(6)) molecules in an external quadrupole static attraction ion trap. The hydrogen- and boron-contents of the B(10-y)H(x) (+) cluster are controlled by charge transfer from ambient gas ions. In the process of ionization, a certain number of hydrogen and boron atoms are detached from decaborane ions by the energy caused by charge transfer. The energy caused by the ion-molecule reactions also induces H atom detachment. Ambient gas of Ar leads to the selective generation of B(10)H(6) (+). The B(10)H(6) (+) clusters react with B(2)H(6) molecules, resulting in the selective formation of B(12)H(8) (+) clusters. Ambient gas of Ne (He) leads to the generation of B(10-y)H(x) (+) clusters with x=4-10 and y=0-1 (with x=2-10 and y=0-2), resulting in the formation of B(12)H(n) (+) clusters with n=4-8 (n=2,4-8). The introduction of ambient gas also increases the production of clusters. PBE0/6-311+G(d)//B3LYP/6-31G(d)-level density functional theory calculations are conducted to investigate the structure and the mechanism of formation of B(10-y)H(x) (+) and B(12)H(n) (+) clusters.
我们通过在外加的四极静电吸引离子阱中分解和离子-分子反应研究了十硼烷（B(10)H(14)）和乙硼烷（B(2)H(6)）分子形成含氢量可控的 B(12)H(n)(+)团簇。B(10-y)H(x)(+)团簇中的氢和硼含量通过环境气体离子的电荷转移来控制。在电离过程中，十硼烷离子通过电荷转移产生的能量会使一定数量的氢和硼原子脱离。离子-分子反应产生的能量也会导致 H 原子脱离。环境气体 Ar 会选择性地生成 B(10)H(6)(+)。B(10)H(6)(+)团簇与 B(2)H(6)分子反应，选择性地生成 B(12)H(8)(+)团簇。环境气体 Ne（He）会生成 x=4-10，y=0-1（x=2-10，y=0-2）的 B(10-y)H(x)(+)团簇，导致 B(12)H(n)(+)团簇形成，n=4-8（n=2，4-8）。引入环境气体也会增加团簇的生成。采用 PBE0/6-311+G(d)//B3LYP/6-31G(d)密度泛函理论计算研究了 B(10-y)H(x)(+)和 B(12)H(n)(+)团簇的结构和形成机制。
