Theoretical prediction of the linear isomers for rare gas-carbon disulfide complexes : He-CS2, Ne-CS2, and Ar-CS2

• Main Authors: Zang, Limin, Dai, Wei, Zheng, Limin, Duan, Chuanxi, Lu, Yunpeng, Yang, Minghui
• Other Authors: School of Physical and Mathematical Sciences
• Format: Article
• Language: English
• Published: 2014
• Subjects: DRNTU::Science::Chemistry::Physical chemistry
• Online Access: https://hdl.handle.net/10356/104011; http://hdl.handle.net/10220/19498
• Institution: Nanyang Technological University

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.