We present new measurements of differential cross sections for the optical collision process for an extended range of optical detunings. A combined analysis of the present scattering results and the earlier NaNe laser-spectroscopic data by Lapatovich et al (1980 J. Chem. Phys. 73 5419) for optical transitions A-X and B-X is performed using a coupled channels approach in both cases. We obtain the Born–Oppenheimer potentials for the ground state and the excited states and as well as the diagonal and off-diagonal spin-orbit functions of the NaNe van der Waals molecule for a wide range of atomic distances.