A new ab initio potential energy surface and infrared spectra for the Ar-CS₂ complex.

Abstract

We report a new three-dimensional potential energy surface for Ar-CS2 involving the Q3 normal mode for the υ3 antisymmetric stretching vibration of the CS2 molecule. The potential energies were calculated using the supermolecular method at the coupled-cluster singles and doubles level with noniterative inclusion of connected triples, using augmented correlation-consistent quadruple-zeta basis set plus midpoint bond functions. Two vibrationally averaged potentials with CS2 at both the ground (υ = 0) and the first excited (υ = 1)υ3 vibrational states were generated from the integration of the three-dimensional potential over the Q3 coordinate. Each potential was found to have a T-shaped global minimum and two equivalent linear local minima. The radial discrete variable representation /angular finite basis representation method and the Lanczos algorithm were applied to calculate the rovibrational energy levels. The calculated band origin shift of the complex (0.0622 cm(-1)) is very close to the observed one (0.0671 cm(-1)). The predicted infrared spectra and spectroscopic parameters based on the two averaged potentials are in excellent agreement with the available experimental data.