Laboratoire de Physique des Lasers, Atomes et Molécules, UMR CNRS 8523, Université de Lille 1, F-59655 Villeneuve d'Ascq, France.
J Phys Chem A. 2010 Mar 4;114(8):2794-8. doi: 10.1021/jp912082b.
The millimeter-wave rotational spectrum of ethanetellurol has been recorded and assigned for the first time. The spectroscopic study has been complemented by high level ab initio calculations. Geometries, total electronic energies, and harmonic vibrational frequencies have been determined at the MP2 level. A small-core relativistic pseudopotential basis set (cc-pVTZ-PP) was employed to describe the tellurium atom. Two stable conformers, synclinal and antiperiplanar, have been identified. Both theory and experiment have shown the synclinal form to be more stable by 2 kJ/mol. The doublet structure observed in the rotational spectrum of synclinal conformer is attributed to tunneling motion of tellurol functional group. The energy difference between 0(+) and 0(-) substates split by tunneling has been determined from the observed spectra.
首次记录并分配了乙硫醇的毫米波旋转光谱。该光谱研究还辅以高级别从头算计算。在 MP2 水平上确定了几何形状、总电子能量和简谐振动频率。采用小核相对论赝势基组（cc-pVTZ-PP）来描述碲原子。已确定了两种稳定构象，顺式和反式。理论和实验都表明顺式构象更稳定，相差 2 kJ/mol。在顺式构象的旋转光谱中观察到的双峰结构归因于碲醇官能团的隧道运动。从观察到的光谱中确定了隧道分裂 0(+)和 0(-)亚态之间的能量差。
