Effect of photochemistry on molecular detection by cavity ringdown spectroscopy: case study of an explosive-related compound

Explosives and explosive-related compounds usually have dissociative excited electronic states. We consider the effect of excited-state dissociation upon an absorption event on the UV cavity ringdown spectroscopy (CRDS) detection of these molecules. A change in the photon decay lifetime with increasing laser energy is demonstrated with vapors of 2,6-dinitrotoluene in the open atmosphere. The magnitude of the effect is modeled with coupled equations describing the time-dependent light intensity and molecular concentration within the cavity. The light intensities required within this model to explain the observed changes in the photon decay lifetimes are consistent with the light intensities expected within the cavity under our experimental conditions. It was also found that the slow diffusion of the molecules in static air can magnify the effect of photochemistry on UV CRDS trace detection of molecules with dissociative excited states. OCIS codes: 280.3420, 300.1030, 300.6390.