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The spectra of photon yield from solid Xe and Kr were measured in the energy range of absorption of Γ(3/2) n = 1 excitons. Using combination of time-resolved spectroscopy with selective photoexcitation by synchrotron radiation, the creation of free excitons was experimentally separated from direct population of molecular emitting centers. For the first time the threshold of photon absorption by molecular trapped centers is observed in excitation spectra of free exciton luminescence.

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Time-resolved photoluminescence of the exciton emission in rare gas solids has \ een measured for excitation in the range of inner-shell transitions. The excitons are created both 'promptly' (within the experimental time resolution) and 'delayed' through electron-hole recombination. Excitation spectra at the Ad edge in Xe and the 3d edge in Kr are discussed. An outstanding feature of the time resolved spectra is the strong resonance that appears in a short time window above a threshold energy, which is the sum of the ionisation energy of the core level and the energy of the (valence) free exciton.