Rare gas–dihalogen potential energy surfaces
Rare gas–dihalogen potential energy surfaces
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稀有气体-二卤势能面
DOI：
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发表时间：
1999
期刊：
影响因子：
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通讯作者：
K. Janda
中科院分区：
文献类型：
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作者：
A. Rohrbacher;Jason Williams;K. Janda
尽管稀有的气体-卤素相互作用一直是研究最深入的分子间力之一，但直到最近几年，才有定性校正的势能面可用于基电子态。以前，通常使用的是球面原子-原子势，这些势不能解释真实表面的线性最小值。例如，除了远离位势极小值的区域外，HeClF和NeCl2的二维势现在已知得相当精确。这些势的第三个维度，即与稀有气体原子的相互作用与卤素键长的函数关系，仍有待完全研究。对于ArI2来说，即使是表面的质量方面也仍然存在相当大的争议。还研究了稀有气体原子与卤素的B3Π0激发电子态的相互作用。对于这些态，球面原子-原子势要精确得多，并与许多实验数据相一致。然而，势中的非球面项和电子的非绝热效应直到现在才被定量地研究。对于大多数其他电子态，几乎没有进行过定量工作。本综述对这项工作进行了历史回顾，总结了我们的理解现状，并提出了进一步研究的途径。
Even though the rare gas–halogen interactions have been among the most intensively studied intermolecular forces, it is only in the last few years that qualitatively correct potential energy surfaces have become available for the ground electronic states. Previously, spherical atom–atom potentials were commonly used, and these potentials could not account for the linear minima of the true surface. The two dimensional potentials for HeClF and NeCl2, for example, are now known rather precisely except for regions far from the potential minima. The third dimension of these potentials, the dependence of the interaction with the rare gas atom as a function of the halogen bond length, still remains to be completely investigated. For ArI2, even the qualitative aspects of the surface are still in considerable dispute. The interactions of the rare gas atoms with the B3Π0 excited electronic states of the halogens have also been intensively studied. For these states, the spherical atom–atom potentials are much more accurate and produce agreement with much of the experimental data. However, the non-spherical terms in the potential and the effects of electronic non-adiabaticity are only now being quantitatively studied. For most other electronic states, very little quantitative work has been performed. This review gives a historical overview of this work, summarizes the current state of our understanding, and proposes avenues for further investigation.