A uniform flow-cavity ring-down spectrometer (UF-CRDS): A new setup for spectroscopy and kinetics at low temperature.

The UF-CRDS (Uniform Flow-Cavity Ring Down Spectrometer) is a new setup coupling for the first time a pulsed uniform (Laval) flow with a continuous wave CRDS in the near infrared for spectroscopy and kinetics at low temperature. This high resolution and sensitive absorption spectrometer opens a new window into the phenomena occurring within UFs. The approach extends the detection range to new electronic and rovibrational transitions within Laval flows and offers the possibility to probe numerous species which have not been investigated yet. This new tool has been designed to probe radicals and reaction intermediates but also to follow the chemistry of hydrocarbon chains and PAHs which play a crucial role in the evolution of astrophysical environments. For kinetics measurements, the UF-CRDS combines the CRESU technique (French acronym meaning reaction kinetics in uniform supersonic flows) with the SKaR (Simultaneous Kinetics and Ring-Down) approach where, as indicated by its name, the entire reaction is monitored during each intensity decay within the high finesse cavity. The setup and the approach are demonstrated with the study of the reaction between CN (v = 1) and propene at low temperature. The recorded data are finally consistent with a previous study of the same reaction for CN (v = 0) relying on the CRESU technique with laser induced fluorescence detection.

The Water Dimer Investigated in the 2OH Spectral Range Using Cavity Ring-Down Spectroscopy.

Two setups based on CW cavity ring-down spectroscopy were used at Bruxelles and Rennes to record jet-cooled water dimer absorption between 7188 and 7285, and between 7357 and 7386 cm(-1). Some 19 absorption features are reported, significantly more than in the literature. Limited high-resolution information is available due to strong overlap between neighboring vibration-rotation-tunneling (VRT) structures and to spectral broadening induced by short upper state vibrational predissociation lifetimes, likely to range between 100 and 20 ps. Rotational band contours analyses are performed to assign the partly resolved VRT structures to the v1v2v3,vfvb = 000,11; 200,00; 000,20; and 101,00 zero-order vibrational states. Their wavenumbers are found to be 7192.34, 7225.86, 7240.57, and 7256.99 cm(-1), respectively. Both so-called acceptor-switching tunneling components are involved in the assignments whose tentative character is discussed.

Strong thermal nonequilibrium in hypersonic CO and CH4 probed by CRDS.

A new experimental setup coupling a High Enthalpy Source (HES) reaching 2000 K to a cw-cavity ring-down spectrometer has been developed to investigate rotationally cold hot bands of polyatomic molecules in the [1.5, 1.7] µm region. The rotational and vibrational molecular degrees of freedom are strongly decoupled in the hypersonic expansion produced by the HES and probed by cavity ring-down spectroscopy. Carbon monoxide has been used as a first test molecule to validate the experimental approach. Its expansion in argon led to rotational and vibrational temperatures of 6.7 ± 0.8 K and 2006 ± 476 K, respectively. The tetradecad polyad of methane (1.67 µm) was investigated under similar conditions leading to rotational and vibrational temperatures of 13 ± 5 K and 750 ± 100 K, respectively. The rotationally cold structure of the spectra reveals many hot bands involving highly excited vibrational states of methane.