Resonant Photocatalytic Effect in Laser-Induced Unimolecular Decomposition

The probability rate of photon-catalyzed molecular predissociation (or unimolecular reaction) is shown to increase by many orders of magnitude in the case of (near-) resonance of the laser frequency with intermediate discrete molecular states. As a result, the photocatalytic effect is important even at unexpectedly low laser power. Both the resonant and the nonresonant photocatalytic effects can be demonstrated by experiments with alkalimetal dimers (e.g., Na₂).