Laser-induced predissociative fluorescence: dynamics and polarization and the effect of lower-state rotational energy transfer on quantitative diagnostics

Laser-induced predissociative fluorescence is often used for diagnostics because its short-lived upper states are minimally disturbed by collisions. We discuss the effects of lower-state collisions with parameters relevant to our atmospheric H(2)-O(2) flame. A pulse of tunable KrF excimer-laser light induces the A ? X, Q(1)(11), 3 ? 0 transition in OH. We measure the intensity and the polarization of the resulting A ? X, Q(1)(11), 3 ? 2 fluorescence as a function of laser brightness. A simple model that uses no adjustable parameters produces a reasonable fit to the data. It predicts that, even at very modest laser energies, the fluorescence intensity is almost directly proportional to the rate constant for rotational energy transfer (RET) within the lower vibrational state. That rate constant can be a strong function of local conditions. Furthermore, under typical operating conditions the excimer will pump an amount of OH out of the lower state that is many times as large as that originally present. This occurs because RET within the X-state continuously replenishes the lower state during the laser pulse. Even when this occurs, the signal may still vary linearly with laser intensity, and the polarization may be nearly that expected for weak pumping. At the higher laser intensities, a significant fraction of the measured OH arises from two-photon photodissociation of the water from the flame reaction.