小水分子团簇中的重排和隧穿分裂
Rearrangements and Tunneling Splittings in Small Water Clusters
摘要：
最近的远红外振动-旋转隧穿（FIR-VRT）实验对理论提出了新的挑战，因为这种光谱的解释和预测需要详细了解远离最小值的势能面（PES）。特别是我们需要一个完整的反应图方面的PES的全球性描述。因此，所有的过渡态和相关的机制，可能会引起可观察到的隧道劈裂必须加以表征。单从过渡态来猜测原子的详细排列是可能的，但经验表明这是不明智的。在这篇文章中，将简要概述处理此类系统的大振幅运动所涉及的问题，并参考更详细的讨论和一些具体的例子。特别地，我们将考虑有效的分子对称群，重排机制的分类，最小值和过渡态的位置和反应途径的计算。这些理论的应用范围从水二聚体到水六聚体的小水集群，然后将被考虑。更多细节可以在最近的评论中找到。
英文摘要：
Recent far-infrared vibration-rotation tunneling (FIR-VRT) experiments pose new challenges to theory because the interpretation and prediction of such spectra requires a detailed understanding of the potential energy surface (PES) away from minima. In particular we need a global description of the PES in terms of a complete reaction graph. Hence all the transition states and associated mechanisms which might give rise to observable tunneling splittings must be characterized. It may be possible to guess the detailed permutations of atoms from the transition state alone, but experience suggests this is unwise. In this contribution a brief overview of the issues involved in treating the large amplitude motions of such systems will be given, with references to more detailed discussions and some specific examples. In particular we will consider the effective molecular symmetry group, the classification of rearrangement mechanisms, the location of minima and transition states and the calculation of reaction pathways. The application of these theories to small water clusters ranging from water dimer to water hexamer will then be considered. More details can be found in recent reviews.
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