Quantitative nonlinear spectroscopy: a direct comparison of degenerate four-wave mixing with cavity ring-down spectroscopy applied to NaH

Cavity ring-down spectroscopy and degenerate four-wave mixing have been applied for spectroscopic studies, temperature determination, and measurement of relative dipole transition moments of photochemically produced sodium hydride. In our experiment, NaH was formed within a heat-pipe oven after 3p excitation of sodium in a hydrogen atmosphere with a second dye laser. The reaction product NaH was probed in the near ultraviolet part of the spectrum at 382 nm with 1-4-μs delay to the excitation pulse using both a linear and nonlinear spectroscopic technique with a pulsed dye laser source (pulsewidth 15-ns full-width half-maximum). The strengths and limitations of these two spectroscopic techniques are discussed. Since the two processes depend on different parameters and the image-forming beams have different properties, it is difficult to define a single criterion for comparison. But our measurements indicate that cavity ring-down spectroscopy is a powerful tool with a sensitivity better than 10⁹ particles per cm³ and quantum state which is comparable to degenerate four-wave mixing in our case