Key Laboratory of Magnetic Resonance in Biological Systems, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Centre for Magnetic Resonance, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, People's Republic of China.
College of Physical Science and Technology, Central China Normal University, Wuhan 430079, People's Republic of China.
J Chem Phys. 2014 Mar 21;140(11):114310. doi: 10.1063/1.4868325.
Theoretical studies of the potential energy surfaces (PESs) and bound states are performed for rare gas-carbon disulfide complexes, He-CS2, Ne-CS2, and Ar-CS2. Three two-dimensional intermolecular PESs are constructed from ab initio data points which are calculated at the CCSD(T) level with aug-cc-pVTZ basis set supplemented with bond functions. We find that the three PESs have very similar features and each PES can be characterized by a global T-shaped minimum, two equivalent local linear minima, and the saddle points between them. The T-shaped isomer is energetically more stable than the linear isomer for each complex. The linear isomers, which have not been observed in experiment so far, are predicted from our PESs and further identified by bound state calculations. Moreover, we assign several intermolecular vibrational states for both the T-shaped and linear isomers of the three complexes via the analysis of wavefunctions. The corresponding vibrational frequencies are calculated from the bound state energies for these assigned states. These frequencies could be helpful for further experimental studies, especially for the linear isomers. We also calculate the rovibrational transition frequencies for the three T-shaped isomers and the pure rotational transition frequencies for the linear isomers, respectively. The accuracy of the PESs is validated by the good agreement between theoretical and experimental results for the rovibrational transition frequencies and spectroscopic parameters.
对稀有气体-二硫化碳复合物（He-CS2、Ne-CS2 和 Ar-CS2）的势能面（PES）和束缚态进行了理论研究。从从头算数据点构建了三个二维分子间 PES，这些数据点是在 CCSD(T)水平上用 aug-cc-pVTZ 基组加上键函数计算得到的。我们发现三个 PES 具有非常相似的特征，每个 PES 都可以用全局 T 形最小值、两个等效的局部线性最小值和它们之间的鞍点来表征。T 形异构体对于每个复合物都比线性异构体更稳定。线性异构体目前尚未在实验中观察到，从我们的 PES 预测，并通过束缚态计算进一步识别。此外，我们通过分析波函数为三个复合物的 T 形和线性异构体分配了几个分子间振动状态。从这些分配状态的束缚态能量计算了相应的振动频率。这些频率对于进一步的实验研究可能会有帮助，特别是对于线性异构体。我们还分别计算了三个 T 形异构体的 rovibrational 跃迁频率和线性异构体的纯转动跃迁频率。PES 的准确性通过理论和实验 rovibrational 跃迁频率和光谱参数之间的良好一致性得到验证。
