In a recent paper, we have performed accurate model potential calculations for the adiabatic excited states of the Na2 molecule. In view of dynamical calculations we propose a method to extract doubly excited potential curves, singly excited Rydberg series, and electronic couplings. In contrast to the previous work, the diabatic curves are correctly matching the adiabatic curves at large internuclear distances, and the electronic interactions do vanish in the asymptotic region. The adequacy of scaling laws to extract reduced parameters relevant to MQDT treatment of molecular autoionization is discussed. These parameters are used to calculate cross-sections for the associative ionization reaction at thermal collision energies when fine structure splitting can be neglected. In the framework of a simple model for the treatment of the long range dynamical couplings, we show the strong influence of the initial preparation of the atoms, and of long range population transfers. In contrast to the usual interpretation of experimental data, we predict that at least four doubly excited states may contribute efficiently to the process. Nevertheless, we may reproduce the marked variation of the observed ion signal as a function of the polarization of the exciting light. This work is a step towards a full treatment of the associative ionization between two cold atoms.