Population of the 4d atomic Ne levels by dissociative recombination of Ne//2** plus molecular ions in a decaying plasma is studied for different electron temperatures. Data on the degree of vibrational excitation of Ne//2** plus ion are obtained that show that V-T relaxation occurs via inelastic Ne//2** plus -neon atom collisions at moderately high pressures. The possibility is considered of deducing the interaction potentials for the excited and ground-state atoms from the spectral line intensities as function of the electron temperature during the afterglow.