Two-photon laser-induced fluorescence of H O and D O molecules at ambient pressure

We have carried out experiments of two-photon excitation of vapor phase H₂O and D₂O molecules at atmospheric pressure. A narrow-band tunable UV OPO laser is used in the experiments. Transient B ₁ → B ₁ emission from the excited predissociating state is seen in both cases. The complete B ₁ ← A ₁ fluorescence excitation spectrum in the spectral range of 245-250 nm is measured and compared with theory. It is shown that the predissociation rate increases with the rotational quantum number K' _a > 2 more strongly than with K ^′2 _a . No perturbation effects on the measured LIF spectra are observed at a laser power density below 2 GW/cm². Experimental results indicate a negligible contribution from both molecular association and collisions with atmospheric gases. Only an extremely weak vibrational progression belonging to the second positive system of N₂ has been observed, which appears to be due to energy and charge transfer in N ⁺ ₂ ^* + H ₂ O collisions. Received 25 January 2002 / Received in final form 27 May 2002 Published online 4 March 2003