Department of Chemistry, University of Southern California , Los Angeles, California 90089-0482, United States.
Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University , Atlanta, Georgia 30322, United States.
Chem Rev. 2016 May 11;116(9):4913-36. doi: 10.1021/acs.chemrev.5b00506. Epub 2016 Feb 3.
This Review summarizes recent research on vibrational predissociation (VP) of hydrogen-bonded clusters. Specifically, the focus is on breaking of hydrogen bonds following excitation of an intramolecular vibration of the cluster. VP of the water dimer and trimer, HCl clusters, and mixed HCl-water clusters are the major topics, but related work on hydrogen halide dimers and trimers, ammonia clusters, and mixed dimers with polyatomic units are reviewed for completion and comparison. The theoretical focus is on generating accurate potential energy surfaces (PESs) that can be used in detailed dynamical calculations, mainly using the quasiclassical trajectory approach. These PESs have to extend from the region describing large amplitude motion around the minimum to regions where fragments are formed. The experimental methodology exploits velocity map imaging to generate pair-correlated product translational energy distributions from which accurate bond dissociation energies of dimers and trimers and energy disposal in fragments are obtained. The excellent agreement between theory and experiment on bond dissociation energies, energy disposal in fragments, and the contributions of cooperativity demonstrates that it is now possible, with state-of-the-art experimental and theoretical methods, to make accurate predictions about dynamical and energetic properties of dissociating clusters.
这篇综述总结了近期关于氢键团簇的振动预解离（VP）的研究。具体来说，重点是研究在团簇的分子内振动激发后氢键的断裂。水二聚体和三聚体、HCl 团簇以及混合 HCl-水团簇是主要研究对象，但也综述了相关的氢卤化物二聚体和三聚体、氨团簇以及与多原子单元的混合二聚体的研究工作，以完成和比较。理论重点是生成可用于详细动力学计算的准确势能面（PES），主要使用准经典轨迹方法。这些 PES 必须从描述围绕最小值的大振幅运动的区域扩展到形成碎片的区域。实验方法利用速度映射成像从对相关的产物平移动能分布中生成，从而获得二聚体和三聚体的准确键解离能以及碎片中的能量耗散。键解离能、碎片中的能量耗散以及协同作用的贡献在理论和实验之间的极好一致性表明，现在已经有可能通过最先进的实验和理论方法，对解离团簇的动力学和能量性质做出准确的预测。
