Theoretical pressure and dielectric second virial coefficients of CO–Ar

Abstract

Using coupled cluster singles and doubles linear response theory and the d-aug-cc-pVTZ basis set extended with a 3s3p2d1f1g set of midbond functions, the interaction induced electric dipole polarisability surface of the CO–Ar van der Waals complex is computed. Combining this surface with accurate intermolecular potential energy and electric dipole surfaces, the pressure and dielectric second virial coefficients of the complex are calculated by a classical statistical approach. Excellent agreement with experimental results (to within the experimental error bars) is obtained for the pressure second virial coefficient over a range of temperatures. No previous experimental or theoretical investigations have been carried out for the dielectric second virial coefficient, B ε(T), which is estimated to be about 1.9 cm6 mol− 1 at room temperature. This value results from a balance of terms due to the interaction induced electric dipole polarisability (predominant at high temperatures) and orientational electric dipole contributions.