Two molecules showing photochemistry but no fluorescence have been investigated at 80 K in a rigid matrix regarding the behavior of the quantum yield for bond fragmentation as a function of the vibrational/vibronic level and electronic excited state. A new equation was developed to determine the photochemical quantum yield under ambient conditions (80 K). The levels/bands involved were those within a given vibrational progression, in different progressions as well as in combination. The yield was low (Φ = 0.1) with excitation into the n = 0 level of S₁ but very rapidly increased with excitation into higher levels whether they were harmonics or combination levels. A parallel result was observed upon excitation into S₂. Vibrational relaxation/deactivation occurs only between levels of the same vibrational progression. Deactivation from the 0 level of S₂ does not occur via levels of S₁. The photochemically active modes correspond to the vibrational modes present in the region of the molecule where bond breakage occurs. These results add further proof of the complex nature and number of processes that can occur within excited states of photochemically active molecules.