The luminescence spectroscopy of atomic zinc isolated in the solid rare gases (ZnRG) is compared with theoretical predictions obtained with the use of diatomic Zn·RG potentials. In particular, the existence of pairs of emission bands, both of which are assigned to the same gas-phase electronic transition, is examined with the use of diatomic pair potentials to simulate the potential-energy surfaces of the Jahn-Teller active vibrational modes of Zn in the solid. The close agreement found between theory and experiment indicates the validity of the use of pair potentials in the analysis of matrix zinc spectroscopy. Thus, it allows identification of the high-energy emission bands in the ZnRG systems as arising from motions of the rare-gas atoms surrounding the atomic zinc guest and the lower-energy bands as associated with the motion of the zinc atom into an octahedral interstitial site in the lattice.