The anisotropic potentials of He–N2, Ne–N2, and Ar–N2

Abstract

The anisotropic potentials of He–N2, Ne–N2, and Ar–N2 are predicted using the Tang–Toennies potential model. This model damps the long-range ab initio dispersion terms individually using a universal damping function and adds to this a simple Born–Mayer repulsive term. The Born–Mayer parameters for the three systems were derived from SCF calculations. The dispersion coefficients were estimated from established combining rules using an effective multipole spectrum for the N2 molecule computed by Visser and Wormer from the time-dependent coupled Hartree–Fock approximation. The resulting potentials were used to predict the second interaction virial coefficients for each system, and they are found to be in excellent agreement with experiment. It is concluded that the spherical symmetric potentials are within 2%–3% of the true potentials. Some discrepancies with recent molecular beam experiments appear to be present, however, for the anisotropies especially in the case of He–N2. Finally, it is found that the law of corresponding states for anisotropic systems, which predicts that the reduced shapes of the potentials for a given geometrical configuration are identical, also holds for the highly anisotropic rare gas–N2 systems.