Doppler-free saturated-absorption Lamb dips were measured at sub-Pa pressures on rovibrational lines of H₂¹⁶O near 7180 cm⁻¹, using optical feedback frequency stabilized cavity ring-down spectroscopy. The saturation of the considered lines is so high that at the early stage of the ring down, the cavity loss rate remains unaffected by the absorption. By referencing the laser source to an optical frequency comb, transition frequencies are determined down to 100 Hz precision and kHz accuracy. The developed setup allows resolving highly K-type blended doublets separated by about 10 MHz (to be compared to a HWHM Doppler width on the order of 300 MHz). A comparison with the most recent spectroscopic databases is discussed. The determined K-type splittings are found to be very well predicted by the most recent variational calculations.

The amplitude, the temperature dependence, and the physical origin of the water vapour absorption continuum are a long-standing issue in molecular spectroscopy with direct impact in atmospheric and planetary sciences. In recent years, we have determined the self-continuum absorption of water vapour at different spectral points of the atmospheric windows at 4.0, 2.1, 1.6, and 1.25 µm, by highly sensitive cavity-enhanced laser techniques. These accurate experimental constraints have been used to adjust the last version (3.2) of the semi-empirical MT_CKD model (Mlawer-Tobin_Clough-Kneizys-Davies), which is widely incorporated in atmospheric radiative-transfer codes. In the present work, the self-continuum cross-sections, C_S, are newly determined at 3.3 µm (3007 cm⁻¹) and 2.0 µm (5000 cm⁻¹) by optical-feedback-cavity enhanced absorption spectroscopy (OFCEAS) and cavity ring-down spectroscopy (CRDS), respectively. These new data allow extending the spectral coverage of the 4.0 and 2.1 µm windows, respectively, and testing the recently released 3.2 version of the MT_CKD continuum. By considering high temperature literature data together with our data, the temperature dependence of the self-continuum is also obtained.

Fully quantum ab initio calculations of the collision-induced shapes of two rovibrational ${\mathrm{H}}_2$ lines perturbed by He provide an unprecedented subpercent agreement with ultra-accurate cavity-enhanced measurements. This level of consistency between theory and experiment hinges on a highly accurate potential energy surface and a realistic treatment of the velocity changing and dephasing collisions. In addition to the fundamental importance, these results show that ab initio calculations can provide reference data for spectroscopic studies of planet atmospheres at the required accuracy level and can be used to populate spectroscopic line-by-line databases.

The Doppler broadened R(0) and R(1) lines of the (2–0) vibrational band of HD have been measured at liquid nitrogen temperature. The corresponding transitions frequencies are determined with an accuracy of a few tens of kHz.

Ozone formation and depletion play a key role in various physical and chemical atmospheric processes which remain to be understood in more detail. The modeling of such phenomena based on ozone dynamics calculations requires a detailed knowledge of quantum states, transition probabilities, and ozone potential energy surface (PES) near the dissociation threshold $D_0$. Knowledge of highly excited rovibrational states with energies approaching $D_0$ is necessary for a reliable interpretation of satellite measurements of the ozone absorption or emission in the upper atmosphere in nonlocal thermodynamic equilibrium conditions. In addition, these states provide an ideal probe of PESs computed by ab initio methods but their detection by absorption spectroscopy is particularly challenging due to the sharp decrease of the intensity with the energy of the corresponding vibrational combination and overtone bands. In this work, two very high-energy vibrational bands are detected by high sensitivity cavity ring-down spectroscopy providing a noise equivalent absorption ${\alpha }_{\min }$ on the order of a few ${10}^{-11}\mathrm{c}{\mathrm{m}}^{-1}$. The corresponding cold bands, assigned as ${\nu }_1+6{\nu }_2+3{\nu }_3$ and $6{\nu }_1+{\nu }_2+{\nu }_3$ centered at 7969 and $7993\mathrm{c}{\mathrm{m}}^{-1}$, respectively, are about nine orders of magnitude less intense than the well-known ${\nu }_3$ fundamental band near 10 µm. The spectrum analysis allowed for the experimental determination of 240 rovibrational energy levels of the upper vibrational states. The corresponding rotational patterns, located between 93.1% and 96.7% of the dissociation threshold, are the most excited ones measured so far by absorption spectroscopy. The values of the band centers and rotational constants derived from the spectrum analysis provide further confirmation of the absence of an activation barrier on the minimum-energy path towards the dissociation threshold [Tyuterev et al., Phys. Rev. Lett. 113, 143002 (2014)]. The vibrational dynamics is discussed in the context of the radiative transition probabilities and related Einstein coefficients for the observed bands. Another important question in the context of the nuclear dynamics concerns the interaction among the three identical potential wells of the ozone molecule in the ground electronic state, which appears to be due to the Jahn-Teller effect. Recent theoretical results accounting for the three potential wells in a full symmetry approach predicted that vibration states should exhibit deviations from the conventional one-potential-well ab initio calculations, near the dissociation threshold. In the present work, we observe a better agreement of the experimentally determined energy value with the three-wells prediction for the (1,6,3) vibrational state involving a large simultaneous excitation of both bending (${\upsilon }_2=6$) and asymmetric stretch (${\upsilon }_3=3$) vibrations pointing towards a nearby well. This could be tentatively interpreted as a manifestation of the three-wells effect.

The ν₁ fundamental band of N₂O is examined by a novel spectrometer that relies on the frequency locking of an external-cavity quantum cascade laser around 7.8 μm to a near-infrared Tm:based frequency comb at 1.9 μm. Due to the large tunability, nearly 70 lines in the 1240 – 1310 cm⁻¹ range of the ν₁ band of N₂O, from P(40) to R(31), are for the first time measured with an absolute frequency calibration and an uncertainty from 62 to 180 kHz, depending on the line. Accurate values of the spectroscopic constants of the upper state are derived from a fit of the line centers (rms ≈ 4.8 × 10⁻⁶ cm⁻¹ or 144 kHz). The ν₁ transitions presently measured in a Doppler regime validate high accuracy predictions based on sub-Doppler measurements of the ν₃ and ν₃-ν₁ transitions.