Dual-comb spectroscopy of ammonia formation in non-thermal plasmas.

Plasma-activated chemical transformations promise the efficient synthesis of salient chemical products. However, the reaction pathways that lead to desirable products are often unknown, and key quantum-state-resolved information regarding the involved molecular species is lacking. Here we use quantum cascade laser dual-comb spectroscopy (QCL-DCS) to probe plasma-activated NH3 generation with rotational and vibrational state resolution, quantifying state-specific number densities via broadband spectral analysis. The measurements reveal unique translational, rotational and vibrational temperatures for NH3 products, indicative of a highly reactive, non-thermal environment. Ultimately, we postulate on the energy transfer mechanisms that explain trends in temperatures and number densities observed for NH3 generated in low-pressure nitrogen-hydrogen (N2-H2) plasmas.

Mid-infrared supermirrors with finesse exceeding 400 000.

For trace gas sensing and precision spectroscopy, optical cavities incorporating low-loss mirrors are indispensable for path length and optical intensity enhancement. Optical interference coatings in the visible and near-infrared (NIR) spectral regions have achieved total optical losses below 2 parts per million (ppm), enabling a cavity finesse in excess of 1 million. However, such advancements have been lacking in the mid-infrared (MIR), despite substantial scientific interest. Here, we demonstrate a significant breakthrough in high-performance MIR mirrors, reporting substrate-transferred single-crystal interference coatings capable of cavity finesse values from 200 000 to 400 000 near 4.5 µm, with excess optical losses (scatter and absorption) below 5 ppm. In a first proof-of-concept demonstration, we achieve the lowest noise-equivalent absorption in a linear cavity ring-down spectrometer normalized by cavity length. This substantial improvement in performance will unlock a rich variety of MIR applications for atmospheric transport and environmental sciences, detection of fugitive emissions, process gas monitoring, breath-gas analysis, and verification of biogenic fuels and plastics.

Direct frequency comb spectroscopy of HCN to evaluate line lists.

We report direct frequency comb spectroscopy of the 2ν1 band of H13CN in the short-wave infrared (λ = 1.56 µm) towards experimental validation of molecular line lists that support observatories like JWST. The laboratory measurements aim to test spectral reference data generated from an experimentally accurate potential energy surface (PES) and an ab initio dipole moment surface (DMS) calculated from quantum chemistry theory. Benchmarking theory with experiment will improve confidence in new astrophysics and astrochemistry inferred from spectroscopic observations of HCN and HNC. Here we describe our instrumentation and initial results using a cross-dispersed spectrometer with a virtually imaged phased array (VIPA).

Dual electro-optic frequency comb photonic thermometry.

We report a precision realization of photonic thermometry using dual-comb spectroscopy to interrogate a π-phase-shifted fiber Bragg grating. We achieve readout stability of 7.5 mK at 1 s and resolve temperature changes of similar magnitude-sufficient for most industrial applications. Our dual-comb approach enables rapid sensing of dynamic temperature, and our scalable and reconfigurable electro-optic generation scheme enables a broad sensing range without laser tuning. Reproducibility on the International Temperature Scale of 1990 is tested, and ultimately limited by the frequency reference and check-thermometer stability. Our demonstration opens the door for a universal interrogator deployable to multiple photonic devices in parallel to potentially unravel complex multi-physical quantity measurements.

Dual-comb cavity ring-down spectroscopy.

Cavity ring-down spectroscopy is a ubiquitous optical method used to study light-matter interactions with high resolution, sensitivity and accuracy. However, it has never been performed with the multiplexing advantages of direct frequency comb spectroscopy without significantly compromising spectral resolution. We present dual-comb cavity ring-down spectroscopy (DC-CRDS) based on the parallel heterodyne detection of ring-down signals with a local oscillator comb to yield absorption and dispersion spectra. These spectra are obtained from widths and positions of cavity modes. We present two approaches which leverage the dynamic cavity response to coherently or randomly driven changes in the amplitude or frequency of the probe field. Both techniques yield accurate spectra of methane-an important greenhouse gas and breath biomarker. When combined with broadband frequency combs, the high sensitivity, spectral resolution and accuracy of our DC-CRDS technique shows promise for applications like studies of the structure and dynamics of large molecules, multispecies trace gas detection and isotopic composition.

Optical feedback linear cavity enhanced absorption spectroscopy.

A simple and universal technique for performing optical feedback cavity enhanced absorption spectroscopy with a linear Fabry-Pérot cavity is presented. We demonstrate through both theoretical analysis and experiment that a diode laser can be sequentially stabilized to a series of cavity modes without any influence from the direct reflection if the feedback phase is appropriately controlled. With robust handling of the feedback phase and help from balanced detection, a detection limit of 1.3 × 10-9 cm-1 was achieved in an integration time of 30 s. The spectrometer performance enabled precision monitoring of atmospheric methane (CH4) concentrations over a time period of 72 h.

Frequency stabilization of a quantum cascade laser by weak resonant feedback from a Fabry-Perot cavity.

Frequency-stabilized mid-infrared lasers are valuable tools for precision molecular spectroscopy. However, their implementation remains limited by complicated stabilization schemes. Here we achieve optical self-locking of a quantum cascade laser to the resonant leak-out field of a highly mode-matched two-mirror cavity. The result is a simple approach to achieving stable frequencies from high-powered mid-infrared lasers. For short time scales (<0.1ms), we report a linewidth reduction factor of 3×10-6 to a linewidth of 12 Hz. Furthermore, we demonstrate two-photon cavity-enhanced absorption spectroscopy of an N2O overtone transition near a wavelength of 4.53 µm.

Near-infrared cavity ring-down spectroscopy measurements of nitrous oxide in the (4200)←(0000) and (5000)←(0000) bands.

Using frequency-agile rapid scanning cavity ring-down spectroscopy, we measured line intensities and line shape parameters of 14N2 16O in air in the (4200)←(0000) and (5000)←(0000) bands near 1.6 µm. The absorption spectra were modeled with multi-spectrum fits of Voigt and speed-dependent Voigt profiles. The measured line intensities and air-broadening parameters exhibit deviations of several percent relative to values provided in HITRAN 2016. Our measured intensities for these two bands have relative combined standard uncertainties of ∼1% which is approximately five times smaller than literature values. Comparison of the present air-broadening and speed-dependent broadening parameters to experimental literature values for other rotation-vibration bands of N2O indicates significant differences in magnitude and J-dependence. For applications requiring high spectral fidelity, these results suggest that the assumption of band-independent line shape parameters is not appropriate.

Radiocarbon age is just a number.

The idea of radiocarbon existing at equilibrium within Earth's atmosphere has established radiocarbon dating. Adam Fleisher takes a look at its beginnings, achievements and limitations.

Absolute 13C/12C Isotope Amount Ratio for Vienna Pee Dee Belemnite from Infrared Absorption Spectroscopy.

Measurements of isotope ratios are predominantly made with reference to standard specimens that have been characterized in the past. In the 1950s, the carbon isotope ratio was referenced to a belemnite sample collected by Heinz Lowenstam and Harold Urey1 in South Carolina's Pee Dee region. Due to the exhaustion of the sample since then, reference materials that are traceable to the original artefact are used to define the Vienna Pee Dee Belemnite (VPDB) scale for stable carbon isotope analysis2. However, these reference materials have also become exhausted or proven to exhibit unstable composition over time3, mirroring issues with the international prototype of the kilogram that led to a revised International System of Units4. A campaign to elucidate the stable carbon isotope ratio of VPDB is underway5, but independent measurement techniques are required to support it. Here we report an accurate value for the stable carbon isotope ratio inferred from infrared absorption spectroscopy, fulfilling the promise of this fundamentally accurate approach6. Our results agree with a value recently derived from mass spectrometry5, and therefore advance the prospects of SI-traceable isotope analysis. Further, our calibration-free method could improve mass balance calculations and enhance isotopic tracer studies in CO2 source apportionment.

Improvement of the spectroscopic parameters of the air- and self-broadened N2O and CO lines for the HITRAN2020 database applications.

This paper outlines the major updates of the line-shape parameters that were performed for the nitrous oxide (N2O) and carbon monoxide (CO) molecules listed in the HITRAN2020 database. We reviewed the collected measurements for the air- and self-broadened N2O and CO spectra to determine proper values for the spectroscopic parameters. Careful comparisons of broadening parameters using the Voigt and speed-dependent Voigt line-shape profiles were performed among various published results for both N2O and CO. Selected data allowed for developing semi-empirical models, which were used to extrapolate/interpolate existing data to update broadening parameters of all the lines of these molecules in the HITRAN database. In addition to the line broadening parameters (and their temperature dependences), the pressure shift values were revised for N2O and CO broadened by air and self for all the bands. The air and self speed-dependence of the broadening parameter for these two molecules were added for every transition as well. Furthermore, we determined the first-order line-mixing parameters using the Exponential Power Gap (EPG) scaling law. These new parameters are now available at HITRAN online.

Cavity ring-down spectroscopy of CO2 near λ = 2.06 µm: Accurate transition intensities for the Orbiting Carbon Observatory-2 (OCO-2) "strong band".

The λ = 2.06 µm absorption band of CO2 is widely used for the remote sensing of atmospheric carbon dioxide, making it relevant to many important top-down measurements of carbon flux. The forward models used in the retrieval algorithms employed in these measurements require increasingly accurate line intensity and line shape data from which absorption cross-sections can be computed. To overcome accuracy limitations of existing line lists, we used frequency-stabilized cavity ring-down spectroscopy to measure 39 transitions in the 12C16O2 absorption band. The line intensities were measured with an estimated relative combined standard uncertainty of u r = 0.08 %. We predicted the J-dependence of the measured intensities using two theoretical models: a one-dimensional spectroscopic model with Herman-Wallis rotation-vibration corrections, and a line-by-line ab initio dipole moment surface model [Zak et al. JQSRT 2016;177:31-42]. For the second approach, we fit only a single factor to rescale the theoretical integrated band intensity to be consistent with the measured intensities. We find that the latter approach yields an equally adequate representation of the fitted J-dependent intensity data and provides the most physically general representation of the results. Our recommended value for the integrated band intensity equal to 7.183 × 10-21 cm molecule-1 ± 6 × 10-24 cm molecule-1 is based on the rescaled ab initio model and corresponds to a fitted scale factor of 1.0069 ± 0.0002. Comparisons of literature intensity values to our results reveal systematic deviations ranging from -1.16 % to +0.33 %.

Doppler-Free Two-Photon Cavity Ring-Down Spectroscopy of a Nitrous Oxide (N2O) Vibrational Overtone Transition.

We report Doppler-free two-photon absorption of N2O at λ = 4.53 µm, measured by cavity ring-down spectroscopy. High power was achieved by optical self-locking of a quantum cascade laser to a linear resonator of finesse F = 22730 , and accurate laser detuning over a 400 MHz range was measured relative to an optical frequency comb. At a sample pressure of p = 0.13 kPa, we report a large two-photon cross-section per molecule of σ 13 ( 2 ) = 8.0 × 10 - 41 cm4 s for the Q(18) rovibrational transition at a resonant frequency of ν 0 = 66179400.8 MHz.

Precision Spectroscopy of Nitrous Oxide Isotopocules with a Cross-Dispersed Spectrometer and a Mid-Infrared Frequency Comb.

As a potent greenhouse gas and an ozone-depleting agent, nitrous oxide (N2O) plays a critical role in the global climate. Effective mitigation relies on understanding global sources and sinks, which can be supported through isotopic analysis. We present a cross-dispersed spectrometer, coupled with a mid-infrared frequency comb, capable of simultaneously monitoring all singly substituted, stable isotopic variants of N2O. Rigorous evaluation of the instrument lineshape function and data treatment using a Doppler-broadened, low-pressure gas sample are discussed. Laboratory characterization of the spectrometer demonstrates sub-GHz spectral resolution and an average precision of 6.7 × 10-6 for fractional isotopic abundance retrievals in 1 s.

Optical Sensors and Sensing, 2019: introduction to the joint feature issue.

This joint feature issue of Optics Express and Applied Optics highlights contributions from authors who presented their latest research at the OSA Optical Sensors and Sensing Congress, held in San Jose, California, USA from 25-27 June 2019. The joint feature issue comprises 6 contributed papers, which expand upon their respective conference proceedings. The published papers introduced here cover a range of timely research topics in optics and photonics for active open-path sensing, radiometry, and adaptive optics and fiber devices.

Optical Sensors and Sensing 2019: introduction to the joint feature issue.

This joint feature issue of Optics Express and Applied Optics highlights contributions from authors who presented their latest research at the OSA Optical Sensors and Sensing Congress, held in San Jose, California, USA, from 25-27 June 2019. The joint feature issue comprises six contributed papers, which expand upon their respective conference proceedings. The published papers introduced here cover a range of timely research topics in optics and photonics for active open-path sensing, radiometry, and adaptive optics and fiber devices.

High-resolution cavity ring-down spectroscopy of the ν1 + ν6 combination band of methanol at 2.0 µm.

Reported here are portions of the infrared absorption cross section for methanol (CH3OH), as measured by frequency-stabilized cavity ring-down spectroscopy (FS-CRDS) at wavelengths near λ = 2.0 µm. High-resolution spectra of two gravimetric mixtures of CH3OH-in-air with nominal mole fractions of 202.2 µmol/mol and 45.89 µmol/mol, respectively, were recorded at pressures between 0.8 kPa and 102 kPa and at a temperature of 298 K. Covering the experimental wavenumber range of 4990 cm-1 to 5010 cm-1 in increments of 0.0067 cm-1 and with an instrument linewidth of 30 kHz, we observed an evolution in the CH3OH spectrum from resolved absorption lines at a low pressure (0.833 kPa) to a pseudocontinuum of absorption at a near-atmospheric pressure (101.575 kPa). An analysis of resolvable features at the lowest recorded pressure yielded a minimum intramolecular vibrational energy redistribution (IVR) lifetime for the OH-stretch (ν1) plus OH-bend (ν6) combination of τIVR ≥ 232 ps-long compared to other methanol overtones and combinations. Consequently, we show that high-resolution FS-CRDS of this relatively weak CH3OH combination band provided an additional avenue by which to study the intramolecular dynamics of this simplest organic molecule with hindered internal rotation.

Twenty-Five-Fold Reduction in Measurement Uncertainty for a Molecular Line Intensity.

To accurately attribute sources and sinks of molecules like CO_{2}, remote sensing missions require line intensities (S) with relative uncertainties u_{r}(S)<0.1%. However, discrepancies in S of ≈1% are common when comparing different experiments, thus limiting their potential impact. Here we report a cavity ring-down spectroscopy multi-instrument comparison which revealed that the hardware used to digitize analog ring-down signals caused variability in spectral integrals which yield S. Our refined approach improved measurement accuracy 25-fold, resulting in u_{r}(S)=0.06%.

Dual electro-optic frequency comb spectroscopy using pseudo-random modulation.

An approach for dual-comb spectroscopy using electro-optic (EO) phase modulation is reported. Maximum-length pseudo-random binary sequences allow for energy-efficient and flexible comb generation. Self-correction of interferograms is shown to remove relative comb drifts and improve mutual coherence, even for EO combs derived from the same laser source. Methane spectroscopy is reported over a ∼10 GHz spectral range, limited by the modulators' bandwidth. The potential of a simple EO comb instrument is demonstrated to rapidly quantify atmospheric methane emissions with ppb precision over 1 km.