Lamb-dip cavity ring-down spectroscopy of acetylene at 1.4 μm

Doppler-free saturated-absorption Lamb dips are observed for weak vibration-rotation transitions of C2H2 between 7167 and 7217 cm−1, using a frequency-comb assisted cavity ring-down spectrometer based on the use of a pair of phase-locked diode lasers.We measured the absolute center frequency of sixteen lines belonging to the 2ν3 + ν1 5 band, targeting ortho and para states of the molecule. Line pairs of the P and Q branches were selected so as to form a ‘V’-scheme, sharing the lower energy level. Such a choice made it possible to determine the rotational energy separations of the excited vibrational state for J-values from 11 to 20. Line-center frequencies are determined with an overall uncertainty between 3 and 13 kHz. This is over three orders of magnitude more accurate than previous experimental studies in the spectral region around the wavelength of 1.4 μm. The retrieved energy separations provide a stringent test of the so-called MARVEL method recently applied to acetylene

The Boltzmann constant from the shape of a molecular spectral line

We report on our recent determination of the Boltzmann constant, k(B), by means of Doppler broadening thermometry. This relatively new method of primary gas thermometry was implemented by using a pair of offset-frequency locked extended-cavity diode lasers at 1.39 mu m, to probe a particular vibration-rotation transition of the (H2O)-O-18 molecule. Adopting a rather sophisticated and extremely refined line shape model in the spectral analysis procedure, we were able to determine the Doppler width from high-quality absorption spectra with unprecedented accuracy. Our spectroscopic determination of kB exhibits a combined (type A plus type B) uncertainty of 24 parts over 10(6). The complete uncertainty budget is presented and discussed

Water vapor concentration measurements in high purity gases by means of comb assisted cavity ring down spectroscopy

In manufacturing processes of semiconductor industry accurate detection and monitoring of water vapor concentration in trace amount is of great importance. The ability to perform reliable measurements in ultrapure gases, with a wide dynamic range and low uncertainty, can have a substantial impact on product quality and process performances. Here, we report on the development of a second-generation comb-assisted cavity ring-down spectrometer and present H2O mole fraction measurements in high-purity N2 gas. Based on the use of a pair of phase-locked lasers and referenced to an optical frequency comb synthesizer, the spectrometer allowed to record high-quality absorption spectra in coincidence with the 32,2 → 22,1 H2O transition at 1.3946 μm. Retrieval of water mole fractions, at levels as low as 380 part per billion, was accomplished through a careful spectra analysis procedure based on the use of refined line shape models which include speed-dependent effects. Measurements were performed with a statistical reproducibility of 5 parts per billion, for an integration time of about 0.2 s. The noise equivalent and minimum detectable absorption coefficients were found to be 3.1 × 10−11 cm−1/ √ and 6.5 × 10−12 cm−1 , respectively. This latter allowed for a minimum detectable water mole fraction (limit of detection) of 160 parts per trillion. Finally, the main sources of systematic uncertainty have been discussed and quantified.This work was done within the project PROMETH2O (EMPIR 20IND06), which received funding from the EMPIR programme cofinanced by the Participating States and from the European Union's Horizon 2020 research and innovation programme

Cavity-ring-down Doppler-broadening primary thermometry

A step forward in Doppler-broadening thermometry is demonstrated using a comb-assisted cavity-ring-down spectroscopic approach applied to an isolated near-infrared line of carbon dioxide at thermodynamic equilibrium. Specifically, the line-shape of the Pe(12) line of the (30012)â\u86\u90(00001) band of CO2 at 1.578 μm is accurately measured and its Doppler width extracted from a refined multispectrum fitting procedure accounting for the speed dependence of the relaxation rates, which were found to play a role even at the very low pressures explored, from 1 to 7 Pa. The thermodynamic gas temperature is retrieved with relative uncertainties of 8Ã\u9710-6 (type A) and 11Ã\u9710-6 (type B), which ranks the system at the first place among optical methods. Thanks to a measurement time of only â\u89\u885h, the technique represents a promising pathway toward the optical determination of the thermodynamic temperature with a global uncertainty at the 10-6 level

Novel laser-based techniques for monitoring of volcanoes

An overview of novel laser techniques suitable for volcanic monitoring, based on different kinds of infrared laser sources, is presented. Their main advantages and drawbacks are discussed focusing on the achievable sensitivity and precision levels in analysis of gaseous species. Some of the most recent experimental results obtained in laboratory development as well as in field tests of home-built laser spectrometers are reported. New perspectives in optical devices aimed at geochemical and geophysical applications are also considered

Absolute frequency measurements of CHF3 Doppler-free ro-vibrational transitions at 8.6 μm

We report on absolute measurements of saturated-absorption line-center frequencies of room-temperature trifluoromethane using a quantum cascade laser at 8.6 μm and the frequency modulation spectroscopy method. Absolute calibration of the laser frequency is obtained by direct comparison with a mid-infrared optical frequency comb synthesizer referenced to a radio-frequency Rb standard. Several sub-Doppler transitions falling in the v5 vibrational band are investigated at around 1158.9 cm-1 with a fractional frequency precision of 8.6·10-12 at 1-s integration time, limited by the Rb-clock stability. The demonstrated frequency uncertainty of 6.6·10-11 is mainly limited by the reproducibility of the frequency measurements