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The paper is concerned with the processes induced by the trapping of excitons of the neon matrix by impurity centres O and Xe. Binary and triple solutions are studied by a cathodoluminescence spectroscopy method. It is found that the exciton trapping by impurity particles results in an effective dissociation of O molecules, causes an accelerated migration of atoms through the the crystal and a desorption of O, initiates a defect formation in the vicinity of impurity centers and produces a formation of excimer compounds XeO in triple solutions Ne-O -Xe. The mechanisms of these processes associated with the transport of energy of the matrix electronic excitations to an impurity subsystem and its further relaxation are considered. It is shown that all the effects are based on the general principles conditioned by the energy structure and thermophysical characteristics of the Ne matrix- (i) the fast dissipation of exciton excess energy followed by lattice local heating and deformation; (ii) the repulsive behavior of the interaction between Rydberg’s excited impurity center and surrounding atoms of the matrix.