We performed a first principle systematic calculation on the adiabatic potential energy curves (PECs) of alkali metal (M = Rb and Cs) – rare gas (Rg = He, Ne, Ar, Kr, and Xe) van der Waals molecules over a wide range of interatomic distance R. All electron basis sets of triple and quadruple zeta valence quality were used for the He, Ne, Ar and Kr atoms. Scalar relativistic effects were taken into account for the heavy Rb, Cs and Xe atoms by means of Dirac–Fock effective core potentials. The correlated ground state energies have been obtained within the framework of the spin unrestricted open-shell coupled cluster method, with perturbative treatment of triple excitations. The electronic energies were corrected for the basis set superposition error (BSSE) using the counterpoise method. Energies were extrapolated to the complete basis set (CBS) limit using a two-point scheme. The energy convergence towards the CBS limit was monitored by the saturation of the dummy atom basis set that included bond functions centered at the midpoint of the interatomic distance. The ab initio point-wise PEC was followed to small R to the point where the energy was 0.5 Hartree above the dissociation limit. A Morse long-range (MLR, U^M Rg(R)) potential possessing the correct asymptotic behavior at R → ∞ was fitted to the single point energies. The resulting set of fully analytical MLR potentials was then used to evaluate classical collision integrals over a wide range of collision energies. By this means, diffusion coefficients (D^M Rg(T)) were predicted as functions of the translation temperature T ≤ 3000 K. The reliability of the present ab initio U^M Rg(R) and D^M Rg(T) functions was accessed through a comparison with previous theoretical and experimental results.