Frequency chirped Fourier-Transform spectroscopy.

Fast (sub-second) spectroscopy with high spectral resolution is of vital importance for revealing quantum chemistry kinetics of complex chemical and biological reactions. Fourier transform (FT) spectrometers can achieve high spectral resolution and operate at hundreds of ms time scales in rapid-scan mode. However, the linear translation of a scanning mirror imposes stringent time-resolution limitations to these systems, which makes simultaneous high spectral and temporal resolution very difficult. Here, we demonstrate an FT spectrometer whose operational principle is based on continuous rotational motion of the scanning mirror, effectively decoupling the spectral resolution from the temporal one. Furthermore, we show that such rotational FT spectrometer can perform Mid-IR dual-comb spectroscopy with a single comb source, since the Doppler-shifted version of the comb serves as the second comb. In our realization, we combine the advantages of dual-comb and FT spectroscopy using a single quantum cascade laser frequency comb emitting at 8.2 µm as a light source. Our technique does not require any diffractive or dispersive optical elements and hence preserve the Jacquinot's-, Fellgett's-, and Connes'-advantages of FT spectrometers. By integrating mulitple broadband sources, such system could pave the way for applications where high speed, large optical bandwidth, and high spectral resolution are desired.

Femtosecond pulses from a mid-infrared quantum cascade laser.

The quantum cascade laser has evolved to be a compact, powerful source of coherent mid-infrared light; however, its fast gain dynamics strongly restricts the formation of ultrashort pulses. As such, the shortest pulses reported so far were limited to a few picoseconds with some hundreds of milliwatts of peak power, strongly narrowing their applicability for time-resolved and nonlinear experiments. Here we demonstrate an approach capable of producing near-transform-limited subpicosecond pulses with several watts of peak power. Starting from a frequency-modulated phase-locked state, ultrashort high-peak-power pulses are generated via spectral filtering, gain modulation-induced spectral broadening and external pulse compression. We assess their temporal nature by means of a novel asynchronous sampling method, coherent beat note interferometry and interferometric autocorrelation. These results open new pathways for nonlinear physics in the mid-infrared.

Microsecond-Resolved Infrared Spectroscopy on Nonrepetitive Protein Reactions by Applying Caged Compounds and Quantum Cascade Laser Frequency Combs.

Infrared 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 (about 10 ms with 16 cm-1 resolution), 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 nonrepetitive reactions, e.g., induced by caged compounds, were limited to the millisecond time domain. The advent of dual-comb quantum cascade laser now allows for a rapid reaction monitoring in the microsecond 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 by applying the new technique to the α subunit of the inhibiting Gi protein and to the larger protein-protein complex of Gαi with its cognate regulator of G-protein signaling (RGS). We observe good data quality with a 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 microsecond time regime for nonrepetitive biological systems including all GTPases and ATPases.

Frequency noise correlation between the offset frequency and the mode spacing in a mid-infrared quantum cascade laser frequency comb.

The generation of frequency combs in the mid-infrared (MIR) spectral range by quantum cascade lasers (QCLs) has the potential for revolutionizing dual-comb multi-heterodyne spectroscopy in the molecular fingerprint region. However, in contrast to frequency combs based on passively mode-locked ultrafast lasers, their operation relies on a completely different mechanism resulting from a four-wave mixing process occurring in the semiconductor gain medium that locks the modes together. As a result, these lasers do not emit pulses and no direct self-referencing of a QCL comb spectrum has been achieved so far. Here, we present a detailed frequency noise characterization of a MIR QCL frequency comb operating at a wavelength of 8 µm with a mode spacing of ∼7.4 GHz. Using a beat measurement with a narrow-linewidth single-mode QCL in combination with a dedicated electrical scheme, we measured the frequency noise properties of an optical mode of the QCL comb, and indirectly of its offset frequency for the first time, without detecting it by the standard approach of nonlinear interferometry applied to ultrafast mode-locked lasers. In addition, we also separately measured the noise of the comb mode spacing extracted electrically from the QCL. We observed a strong anti-correlation between the frequency fluctuations of the offset frequency and mode spacing, leading to optical modes with a linewidth slightly below 1 MHz in the free-running QCL comb (at 1-s integration time), which is narrower than the individual contributions of the offset frequency and mode spacing that are at least 2 MHz each.

High-resolution and gapless dual comb spectroscopy with current-tuned quantum cascade lasers.

We present gapless, high-resolution absorption and dispersion spectra obtained with quantum cascade laser frequency combs covering 55 cm-1. Using phase-sensitive dual comb design, the comb lines are gradually swept over 10 GHz, corresponding to the free spectral range of the laser devices, by applying a current modulation. We show that with interleaving the spectral point spacing is reduced by more than four orders of magnitude over the full spectral span of the frequency comb. The potential of this technique for high-precision gas sensing is illustrated by measuring the low pressure (107 hPa) absorption and dispersion spectra of methane spanning the range of 1170 cm-1 - 1225 cm-1 with a resolution of 0.001 cm-1.

Single-Shot Sub-microsecond Mid-infrared Spectroscopy on Protein Reactions with Quantum Cascade Laser Frequency Combs.

The kinetic analysis of irreversible protein reactions requires an analytical technique that provides access to time-dependent infrared spectra in a single shot. Here, we present a spectrometer based on dual-frequency-comb spectroscopy using mid-infrared frequency combs generated by quantum cascade lasers. Attenuation of the intensity of the combs by molecular vibrational resonances results in absorption spectra covering 55 cm-1 in the fingerprint region. The setup has a native resolution of 0.3 cm-1, noise levels in the µOD range, and achieves sub-microsecond time resolution. We demonstrate the simultaneous recording of both spectra and transients of the photoactivated proton pump bacteriorhodopsin. More importantly, a single shot, i.e., a single visible light excitation, is sufficient to extract spectral and kinetic characteristics of several intermediates in the bacteriorhodopsin photocycle. This development paves the way for the noninvasive analysis of enzymatic conversions with high time resolution, broad spectral coverage, and minimal sample consumption.

Tunable dispersion compensation of quantum cascade laser frequency combs.

Compensating for group velocity dispersion is an important challenge to achieve stable midinfrared quantum cascade laser (QCL) frequency combs with large spectral coverage. We present a tunable dispersion compensation scheme consisting of a planar mirror placed behind the back facet of the QCL. Dispersion can be either enhanced or decreased depending on the position of the mirror. We demonstrate that the fraction of the comb regime in the dynamic range of the laser increases considerably when the dispersion induced by the Gires-Tournois interferometer compensates the intrinsic dispersion of the laser. Furthermore, it is possible to tune to the offset frequency of the comb with the Gires-Tournois interferometer while the repetition frequency is almost unaffected.

Simultaneous measurement of NO and NO(2) by dual-wavelength quantum cascade laser spectroscopy.

The concept of a multi-wavelength quantum cascade laser emitting at two or more spectrally well-separated wavelengths is highly appealing for applied spectroscopy, as it allows detecting several species with compact and cost-efficient optical setups. Here we present a practical realization of such a dual-wavelength setup, which is based on a room-temperature quantum cascade laser emitting single-mode at 1600 cm-1 and 1900 cm-1 and is thus well-suited for simultaneous NO and NO2 detection. Operated in a time-division multiplexed mode, our spectrometer reaches detection limits of 0.5 and 1.5 ppb for NO2 and NO, respectively. The performance of the system is validated against the well-established chemiluminescence detection while measuring the NOx emissions on an automotive test-bench, as well as upon monitoring the pollution at a suburban site.

Mid-infrared spectroscopy for gases and liquids based on quantum cascade technologies.

In this paper we present two compact, quantum cascade laser absorption spectroscopy based, sensors developed for trace substance detection in gases and liquids. The gas sensor, in its most integrated version, represents the first system combining a quantum cascade laser and a quantum cascade detector. Furthermore, it uses a toroidal mirror cell with a volume of only 40 cm(3) for a path length of up to 4 m. The analytical performance is assessed by the measurements of isotope ratios of CO2 at ambient abundance. For the (13)CO2/(12)CO2 isotope ratio, a measurement precision of 0.2‰ is demonstrated after an integration time of 600 s. For the liquid sensor, a microfluidic system is used to extract cocaine from saliva into a solvent (PCE) transparent in the mid-infrared. This system is bonded on top of a Si/Ge waveguide and the concentration of cocaine in PCE is measured through the interaction of the evanescent part of the waveguide optical mode and the solvent flowing on top. A detection limit of <100 µg mL(-1) was achieved with this system and down to 10 µg mL(-1) with a simplified, but improved system.