Non-linear effects by continuous wave cavity ringdown spectroscopy in jet-cooled NO2

A new method of high resolution cavity ringdown spectroscopy (CRDS) was recently developed in our laboratory, where a narrow line, continuous wave (CW) single-frequency laser is used instead of a pulsed laser. Here, we will first discuss the main differences between the `traditional' pulsed CRDS and CW-CRDS. Then, we will describe our results exploiting the high intracavity power that can be achieved with CW-CRDS. Using a single-mode Ti:Sa laser, we obtained CRDS spectra where the excitation power of a single cavity mode is close to 20 W. In the virtually collisionless regime of a supersonic slit jet, we observed saturation in some of the weak rovibronic transitions of NO₂ around 796 nm, as evidenced by loss of absorption intensity and formation of Doppler-free Lamb dips. In addition, in coincidence with absorption by these near infrared transitions, an appreciable fluorescence signal was detected in the visible range. According to our interpretation, this fluorescence is from NO₂ levels excited by two photons in a stepwise incoherent process, with a strongly allowed second step. Since the fluorescence spectrum has the same lineshapes as the CRDS absorption spectrum, it seems that the first transition step is the one limiting the overall two-step process. In addition, we also observed very narrow fluorescence features, not coincident with any absorption feature. These must be coherent (non-stepwise), Doppler-free, two-photon transitions. Interesting new questions arise from these preliminary data, and we believe that more measurements of this kind will provide new information about the rovibronic states of NO₂ in the dissociation region.