Dynamics of Molecular Reactions in Clusters

加州大学欧文分校的Benny Gerber教授获得了理论与计算化学项目的资助，研究分子反应的动力学。Gerber将研究氢键和范德华团簇中的光化学反应，以及原子与这些团簇的碰撞诱导反应。研究将从四个方面展开：1)研究紫外光激发下氢键团簇可能引发的集体反应；2)团簇类固态和类液态反应性差异；3)被激发原子和分子在团簇中溶剂化的电子弛豫；4)团簇中分子电子基态的光解/重组。将采用经典MD和半经典波包处理相结合的方法。在分子动力学处理中，将采用半经典技术来保持零点能量，对刚性振动模式采用波包，对软振动模式采用经典动力学。簇中的分子反应的研究作为一种获得对溶剂化对化学反应的影响的额外见解的技术是至关重要的。实验和理论条件可以以系统的方式变化，从由几个孤立分子组成的相对较小的簇一直到模拟大块溶液中凝聚态物质的大簇。

Professor Benny Gerber, U. C. Irvine, is supported by a grant from the Theoretical and Computational Chemistry Program to study the dynamics of molecular reactions in clusters. Gerber will study photochemical reactions in hydrogen bonded and in van der Waals cluster as well as collision-induced reactions of atoms with such clusters. Research will be conducted in four areas: 1) The study of possible collective reactions induced by UV excitation of hydrogen bonded clusters; 2) Differences in reactivity between solid-like and liquid-like states of clusters; 3) Electronic relaxation of excited atoms and molecules solvated in clusters; and 4) Photodissociation / recombination on the electronic ground state of molecules in clusters. A combination of classical MD and semiclassical wavepacket treatments will be employed. A semiclassical technique will be used to preserve zero point energy in the molecular dynamics treatments which employs wavepackets for stiff vibrational modes and classical dynamics for soft modes. The study of molecular reactions in clusters is of primary importance as a technique for gaining additional insight into the effects of solvation upon chemical reactions. Experimental and theoretical conditions can be varied in a systematic fashion from relatively small clusters consisting of a few isolated molecules all the way to large clusters which mimic condensed matter in the bulk solution.