烷烃液体中极性分子的电子俘获：稀溶液中的团簇化学
Electron Trapping by Polar Molecules in Alkane Liquids: Cluster Chemistry in Dilute Solution
摘要：
这种分子的单体和小团簇可以在稀烷烃溶液中可逆地捕获导带电子。利用脉冲辐解-瞬态吸收光谱和时间分辨光电导研究了这种捕获的动力学和能量学。结合能，热脱陷率，和吸收光谱的过剩电子附加到单体和多聚体溶质陷阱，并讨论了这些物种的可能结构。观察到Mozumder在1972年预言的“偶极凝聚”（溶质团簇围绕空穴电子逐步生长）。乙腈单体被证明是溶剂化的电子通过其甲基基团，就像烷烃溶剂。电子与CN基团偶极结合; CN基团指向远离空腔的方向。所得到的带负电荷的物质具有0.4 eV的结合能，并吸收红外线。直链脂肪醇分子通过它们的OH基团溶剂化多余的电子;在平衡时，主要的电子陷阱是三聚体或四聚体;这种溶质陷阱的结合能为约1.5。0.8 EV.被较小的团簇捕获与熵相反，熵将平衡推向溶剂阱中的电子。对于醇单体，不会发生捕获;而是发生缓慢的质子转移反应。对于乙腈单体，捕获在能量上是有利的，但热分离很快（大约。1 ns）。
英文摘要：
Monomers and small clusters of such molecules can reversibly trap conduction band electrons in dilute alkane solutions. The dynamics and energetics of this trapping have been studied using pulse radiolysis - transient absorption spectroscopy and time-resolved photoconductivity. Binding energies, thermal detrapping rates, and absorption spectra of excess electrons attached to monomer and multimer solute traps are obtained and possible structures for these species are discussed. "Dipole coagulation" (stepwise growth of the solute cluster around the cavity electron) predicted by Mozumder in 1972 is observed. Acetonitrile monomer is shown to solvate the electron by its methyl group, just like the alkane solvent does. The electron is dipole-bound to the CN group; the latter points away from the cavity. The resulting negatively charged species has a binding energy of 0.4 eV and absorbs in the infrared. Molecules of straight-chain aliphatic alcohols solvate the excess electron by their OH groups; at equilibrium, the predominant electron trap is a trimer or a tetramer; the binding energy of this solute trap is ca. 0.8 eV. Trapping by smaller clusters is opposed by the entropy which drives the equilibrium towards the electron in a solvent trap. For alcohol monomers, the trapping does not occur; a slow proton transfer reaction occurs instead. For acetonitrile monomer, the trapping is favored energetically but the thermal detachment is rapid (ca. 1 ns).
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