UV photolysis of small molecules embedded in rare-gas matrices is examined. We demonstrate that photolysis can be self-limited when products absorb the photolysing radiation. As a result of the rising absorption, in-situ detected luminescence of the photolysis product saturates faster than its concentration. In particular, the present study supports the conclusion that 193 nm photolysis of hydrogen-containing species in Xe matrices produces hydrogen atoms in amounts comparable with the other dissociating part of the precursor. Also, we show that 193 nm radiation activates mobility of hydrogen atoms in annealing, accelerating photochemical processes related to hydrogen mobility. (C) 1998 Elsevier Science B.V. All rights reserved.