Unambiguous assignment of the van der Waals modes of benzene–Ar by analysis of the rotationally resolved UV‐spectra and comparison with multidimensional calculations
Unambiguous assignment of the van der Waals modes of benzene–Ar by analysis of the rotationally resolved UV‐spectra and comparison with multidimensional calculations
复制标题
通过分析旋转分辨紫外光谱并与多维计算进行比较，明确分配苯-Ar的范德华模式
DOI：
10.1063/1.470812
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发表时间：
1996
影响因子：
4.4
通讯作者：
A. Avoird
中科院分区：
文献类型：
--
作者：
E. Riedle;A. Avoird
We present calculations of the van der Waals (vdW) states of electronically excited benzene‐Ar in which the coupling to the vibronic angular momentum of the excited 61 state of benzene is explicitly included. It is predicted, in particular, that the vibrational angular momentum of the degenerate (E1) vdW bending fundamental leads to parallel Coriolis coupling between two substates and consequently to a perturbed rotational structure of the corresponding parallel band in the UV spectrum. A detailed analysis of these bands in the UV spectra of C6H6‐Ar and C6D6‐Ar is given and found to agree with the theory. This yields not only a set of accurate rotational and Coriolis coupling constants, but also an unambiguous assignment of all observed vdW transitions in the UV spectra of these complexes. The vibrational frequencies, the changes of rotational constants upon vdW excitation, and the intensities calculated with some of the available model potentials, and the isotopic shifts in these quantities are in good a...
