Radiocarbon (${}^{14}\mathrm{C}$) concentrations at a 43 parts-per-quadrillion level are measured by using saturated-absorption cavity ringdown spectroscopy by exciting radiocarbon-dioxide (${}^{14}\mathrm{C}{}^{16}\mathrm{O}_2$) molecules at the $4.5\mu \mathrm{m}$ wavelength. The ultimate sensitivity limits of molecular trace gas sensing are pushed down to attobar pressures using a comb-assisted absorption spectroscopy setup. Such a result represents the lowest pressure ever detected for a gas of simple molecules. The unique sensitivity, the wide dynamic range, the compactness, and the relatively low cost of this table-top setup open new perspectives for ${}^{14}\mathrm{C}$-tracing applications, such as radiocarbon dating, biomedicine, or environmental and earth sciences. The detection of other very rare molecules can be pursued as well thanks to the wide and continuous mid-IR spectral coverage of the described setup.

A comprehensive investigation of the frequency-noise spectral density of a free-running midinfrared quantum-cascade laser is presented for the first time. It provides direct evidence of the leveling of this noise down to a white-noise plateau, corresponding to an intrinsic linewidth of a few hundred hertz. The experiment is in agreement with the most recent theory on the fundamental mechanism of line broadening in quantum-cascade lasers, which provides a new insight into the Schawlow-Townes formula and predicts a narrowing beyond the limit set by the radiative lifetime of the upper level.

A sensitive spectroscopic sensor based on a hollow-core fiber-coupled quantum cascade laser (QCL) emitting at 10.54 μm and quartz enhanced photoacoustic spectroscopy (QEPAS) technique is reported. The design and realization of mid-IR fiber and coupler optics has ensured single-mode QCL beam delivery to the QEPAS sensor. The collimation optics was designed to produce a laser beam of significantly reduced beam size and waist so as to prevent illumination of the quartz tuning fork and microresonator tubes. ${\mathrm{SF}}_6$ was selected as the target gas. A minimum detection sensitivity of 50 parts per trillion in 1 s was achieved with a QCL power of 18 mW, corresponding to a normalized noise-equivalent absorption of $2.7\times {10}^{-10}\mathrm{W}·{\mathrm{cm}}^{-1}/{\mathrm{Hz}}^{1/2}$.

We report on a novel approach to cavity ring-down spectroscopy with the sample gas in saturated-absorption regime. This technique allows us to decouple and simultaneously retrieve the empty-cavity background and absorption signal, by means of a theoretical model that we developed and tested. The high sensitivity and frequency precision for spectroscopic applications are exploited to measure, for the first time, the hyperfine structure of an excited vibrational state of O17C12O16 in natural abundance with an accuracy of a few parts in 10-11.

We report on a spectroscopic technique named intracavity quartz-enhanced photoacoustic spectroscopy (I-QEPAS) employed for sensitive trace-gas detection in the mid-infrared spectral region. It is based on a combination of QEPAS with a buildup optical cavity. The sensor includes a distributed feedback quantum cascade laser emitting at 4.33 μm. We achieved a laser optical power buildup factor of ∼500, which corresponds to an intracavity laser power of ∼0.75 W. CO2 has been selected as the target molecule for the I-QEPAS demonstration. We achieved a detection sensitivity of 300 parts per trillion for 4 s integration time, corresponding to a noise equivalent absorption coefficient of 1.4 × 10−8 cm−1 and a normalized noise-equivalent absorption of 3.2 × 10−10 W cm−1 Hz−1/2.

A quartz enhanced photo-acoustic sensor employing a single-mode quantum cascade laser emitting at 3.93 Terahertz (THz) is reported. A custom tuning fork with a 1 mm spatial separation between the prongs allows the focusing of the THz laser beam between them, while preventing the prongs illumination. A methanol transition with line-strength of 4.28 × 10⁻²¹ cm has been selected as target spectroscopic line. At a laser optical power of ∼ 40 μW, we reach a sensitivity of 7 parts per million in 4s integration time, corresponding to a 1σ normalized noise-equivalent absorption of 2 × 10⁻¹⁰ cm⁻¹W/Hz^½.