Optical frequency comb spectroscopy has proven an indispensable tool for high-resolution spectroscopy. QCL frequency combs offer the possibility to explore the mid-infrared spectral range. However, they suffer from large repetition frequencies which make them seemingly unsuitable for high resolution spectroscopy. We present three measurement modes overcoming this limitation. The rapid-sweep technique allows to retrieve the full high-resolution spectrum in 6ms, the step-sweep technique allows for high-resolution spectroscopy with spectral resolution <5e-4 cm-1. As a last technique we present the time-resolved step-sweep approach enabling high-resolution spectra of sub-millisecond-lived samples. It was assessed in a study of cold gases in supersonic beams.

A proof-of-concept of a scanning stand-off dual-comb spectrometer for explosives detection and identification at 3 m distance is demonstrated. Detection of two types of explosives: RDX and PETN on various surfaces was carried out in reflection-absorption and backscattering modes. A scanning area of 18 cm X 18 cm (400 pixels) was covered in ~2.5 sec. Identification method was based on Pearson’s correlation coefficients between the recorded reflection-absorption (backscatter reflection) spectra and transmission (reflection) FTIR of substances, with baseline subtraction using the asymmetric least square smoothing algorithm. Detection limits of the laboratory system of < 2 ug/cm2 were achieved.

To meet the challenges of high-resolution molecular spectroscopy, increasingly sophisticated spectroscopic techniques were developed. For a long time FTIR and laser-based spectroscopies were used for these studies. The recent development of dual-comb spectroscopy at high-resolution makes this technique a powerful tool for gas phase studies. We report on the use and characterization of the IRis-F1, a tabletop mid-infrared dual-comb spectrometer, in the newly developed step-sweep mode. The resolution of the wavenumber axis is increased by step-wise tuning (interleaving) and accurate measurement of the laser center wavelength and repetition frequency. Doppler limited measurements of N2O and CH4 reveal a wavenumber accuracy of 1E-4 cm-1 on the covered range of > 50 cm-1. Measured half-widths of absorption lines show no systematic broadening, indicating a negligible instrument response function. Finally, measurements of nitrogen pressure broadening coefficients in the v4 band of methane show that quantum cascade laser dual-comb spectroscopy in step-sweep mode is well adapted for measurements of precision spectroscopic data, in particular line shape parameters.

Dual frequency comb spectroscopy is used to address limitations of stopped flow infrared spectroscopy, namely, speed, resolution, and the need to repeat reactions to obtain good signal to noise ratios at short timescales.

The identification of explosives residue and other harmful materials in field is a key problem to solve for world safety. Here we present a point-by-point imaging technique based on stand-off dual-comb spectroscopy carried out with QCL frequency combs using a fast scanning technique to provide hyperspectral images with species specific absorption spectra.

For a long time FTIR and laser-based spectroscopies have been used for high resolution molecular spectroscopy studies. The recent development of Dual-Comb Spectroscopy at high resolution (<0.001 cm-1) makes this technique a powerful tool for gas phase studies. The IRis-F1 is a dual-comb spectrometer building on quantum cascade laser frequency combs. We show that it is very well adapted for measurements of line shape parameters. Despite its weak abundance, methane effect on climate and atmospheric chemistry is important. We measured with IRis-F1 the half-widths of absorption lines of methane diluted in nitrogen, and compared with results obtained by other spectroscopies.

ABSTRACTInfrared spectroscopy is ideally suited for the investigation of protein reactions at the atomic level. Many systems were investigated successfully by applying Fourier transform infrared (FTIR) spectroscopy. While rapid-scan FTIR spectroscopy is limited by time resolution (about10 ms with 16 cm-1resolution), step-scan FTIR spectroscopy reaches a time-resolution of about 10 ns but is limited to cyclic reactions that can be repeated hundreds of times under identical conditions. Consequently, FTIR with high time resolution was only possible with photoactivable proteins that undergo a photocycle. The huge number of non-repetitive reactions, e.g. induced by caged compounds, were limited to the ms time domain. The advent of dual comb quantum cascade laser allows now for a rapid reaction monitoring in the μs time domain. Here we investigate the potential to apply such an instrument to the huge class of G-proteins. We compare caged-compound induced reactions monitored by FTIR and dual comb spectroscopy, respectively, by applying the new technique to the α subunit of the inhibiting Giprotein and to the larger protein-protein complex of Gαiwith its cognate regulator of G-protein signaling (RGS). We observe good data quality with 4 μs time resolution with a wavelength resolution comparable to FTIR. This is more than three orders of magnitude faster than any FTIR measurement on G-proteins in the literature. This study paves the way for infrared spectroscopic studies in the so far unresolvable μs time regime for non-repetitive biological systems including all GTPases and ATPases.

A dual-frequency-comb spectrometer based on two quantum-cascade lasers is applied to kinetics studies of formaldehyde (HCHO) in a shock tube. Multispectral absorption measurements are carried out in a broad spectral range of 1740–1790 cm –1 at temperatures of 800–1500 K and pressures of 2–3 bar. The formation of HCHO from thermal decomposition of 1,3,5-trioxane (C 3 H 6 O 3 , 0.9% diluted in argon) and the subsequent oxidation of formaldehyde is monitored with a time resolution of 4 µs. The rate coefficient of the decomposition of C 3 H 6 O 3 (i.e., HCHO formation) is found to be k 1 = 6.0 × 10 15 exp(− 205.58 kJ mol −1 / RT ) s –1 . For the oxidation studies, mixtures of 0.36% C 3 H 6 O 3 and 1% O 2 in argon are used. The information of all laser lines, along with the consideration of individual signal variance of each line, is utilized for kinetic and spectral analysis. The experimental kinetic profiles of HCHO are compared with simulations based on the mechanisms of Zhou et al. (Combust Flame, 197:423–438, 2018) and Cai and Pitsch (Combust Flame, 162:1623–1637, 2015).