Theoretical gas and dielectric second virial coefficients of CO-Ar

Antonio Rizzo (1) , Javier Lopez Cacheiro (2) , Berta Fernandez Rodriguez (2) , Branislav Jansik (3) , Thomas Bondo Pedersen (4)

1 IPCF - CNR Istituto per i Processi Chimico Fisici [Pisa]
2 Chemistry
3 Teoretisk Kemi
4 Theoretical Chemistry

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 polarizability surface of the CO-Ar van der Waals complex is computed. Combining this surface with accurate intermolecular potential energy and electric dipole surfaces, the gas 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 gas second virial coefficient over a range of temperatures. No previous experimental or theoretical investigations have been carried out for the dielectric second virial coefficient, $B_\epsilon(T)$, which is estimated to be about 1.9 cm^6 mol^-1 at room temperature This value results from a balance of terms due to the interaction induced electric dipole polarizability (predominant at high temperatures) and orientational electric dipole contributions.

Mots clés: Physical Sciences

Antonio Rizzo, Javier Lopez Cacheiro, Berta Fernandez Rodriguez, Branislav Jansik, Thomas Bondo Pedersen. Theoretical gas and dielectric second virial coefficients of CO-Ar. Molecular Physics, 2008, 106 (07), pp.881-892. ⟨10.1080/00268970802001363⟩. ⟨hal-00513183⟩