Reactions of large water cluster anions with hydrogen chloride: formation of atomic hydrogen and phase separation in the gas phase.
Reactions of large water cluster anions with hydrogen chloride: formation of atomic hydrogen and phase separation in the gas phase.
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DOI：
10.1021/ja067355o
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发表时间：
2007-02
影响因子：
15
通讯作者：
C. Siu;O. Balaj;V. Bondybey;M. Beyer
中科院分区：
文献类型：
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作者：
C. Siu;O. Balaj;V. Bondybey;M. Beyer
用傅里叶变换离子回旋共振（FT-ICR）质谱法研究了水簇阴离子（H2O）n-, n = 30-70与氯化氢的反应。被团簇吸收的第一个HCl可能是离子溶解的。溶剂化的电子与质子重新结合，从而还原为氢原子并从团簇中蒸发。这一过程伴随着黑体辐射和碰撞引起的水分子损失。随后的碰撞导致HCl的吸收和H2O的损失，产生混合簇Cl-(HCl)m(H2O)n，直到它们被HCl饱和。这些饱和的团簇按一定的顺序失去H2O和HCl。用密度泛函理论计算详细研究了反应的最后阶段，包括m = 0-4和n = 0-6的簇。Cl-(HCl)4(H2O)6簇是气相超分子自组织的一个例子：它由一个四面体Cl-(HCl)4组成，在四面体的一侧连接一个紧凑的水六聚体。
The reactions of water cluster anions (H2O)n-, n = 30-70, with hydrogen chloride have been studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. The first HCl taken up by the clusters is presumably ionically dissolved. The solvated electron recombines with the proton, which is thereby reduced to atomic hydrogen and evaporates from the cluster. This process is accompanied by blackbody radiation and collision induced loss of water molecules. Subsequent collisions lead to uptake of HCl and loss of H2O, yielding mixed clusters Cl-(HCl)m(H2O)n until they are saturated with HCl. Those saturated clusters lose H2O and HCl in a characteristic sequence. The final stage of the reaction, involving clusters with m = 0-4 and n = 0-6, is studied in detail with density functional theory calculations. The Cl-(HCl)4(H2O)6 cluster represents an example for supramolecular self-organization in the gas phase: it consists of a tetrahedral Cl-(HCl)4, connected on one side of the tetrahedron to a compact water hexamer.