Femtosecond two-photon-resonant parametric four-wave mixing detection of atomic hydrogen

We demonstrate an ultrafast parametric four-wave mixing method for the collisional-quenching-free detection of atomic hydrogen. Two photons of 243 nm light resonantly excite the n = 1 to n = 2 transition of atomic hydrogen, and a third probe photon scatters from the electronic coherence to generate the parametric emission of a degenerate signal photon. Laser-induced photofragmentation fluorescence from water, also excited with the same 243 nm pulses, is used as a convenient method to visualize beam overlap in space and time. The femtosecond time resolution enables the suppression of unwanted nonresonant contributions to the signal and separation from resonant mixing in water molecules because of the significantly different coherence lifetimes. A folded BOXCARS phase-matching configuration yields a spatially isolated, laser-like, signal beam, amenable to measurements in highly luminous backgrounds. Measurements in an H₂/CH₄/air flame demonstrate quantitative agreement with simulated H-atom concentration profiles. A coherence decay time constant of 42 ps is recorded in the atmospheric pressure flame.