Kinetics and Mechanism of the Singlet Oxygen Atom Reaction with Dimethyl Ether.

We combine in situ laser spectroscopy, quantum chemistry, and kinetic calculations to study the reaction of a singlet oxygen atom with dimethyl ether. Infrared laser absorption spectroscopy and Faraday rotation spectroscopy are used for the detection and quantification of the reaction products OH, H2O, HO2, and CH2O on submillisecond time scales. Fitting temporal profiles of products with simulations using an in-house reaction mechanism allows product branching to be quantified at 30, 60, and 150 Torr. The experimentally determined product branching agrees well with master equation calculations based on electronic structure data and transition state theory. The calculations demonstrate that the dimethyl peroxide (CH3OOCH3) generated via O-insertion into the C-O bond undergoes subsequent dissociation to CH3O + CH3O through energetically favored reactions without an intrinsic barrier. This O-insertion mechanism can be important for understanding the fate of biofuels leaking into the atmosphere and for plasma-based biofuel processing technologies.

Controlled generation of harmonic states in mid-infrared quantum cascade laser frequency combs by external cavity optical feedback.

We demonstrate the implementation of external cavity optical feedback to improve coherence and promote generation of harmonic states by a mid-infrared quantum cascade laser frequency comb. In particular, we present a Vernier-like scheme to realize harmonic comb states that increase the repetition rate of the comb by a factor of up to 6 and broaden spectral coverages from 46 cm-1 to 92 cm-1. Intermode beatnote and dual comb characterization indicate that the coherence of the comb has greatly improved for sub-optimal devices when the comb is operated in these harmonic states. This approach to control the generation of harmonic states and improve comb performance can be readily incorporated to various sensing systems and has great potential in spectroscopic measurements that require high repetition rates and/or broad optical bandwidth.

Balanced wavelength modulated Zeeman spectroscopy for oxygen detection.

In this paper, we present the development and testing of a balanced Zeeman spectroscopy method utilizing wavelength modulation for selective detection of paramagnetic molecules. We perform balanced detection via differential transmission measurement of right-handed circularly polarized and left-handed circularly polarized light and compare the performance of our system to the Faraday rotation spectroscopy technique. The method is tested using oxygen detection at 762 nm and can provide real-time oxygen or other paramagnetic species detection for a variety of applications.

Compact laser spectroscopic sensor head prototype for time-resolved breath oxygen monitoring.

A small and lightweight optical sensor head prototype with a disposable airway adapter for continuous mainstream monitoring of oxygen at high sampling rate is designed and tested on an optical benchtop. In terms of its size and functionality, the sensor head design is similar to current capnography systems from leading medical equipment manufacturers, and it has been designed within constraints of potential applications in direct breath oxygen monitoring that require direct interaction with the gas inside a breathing tube. The measurement precision of 0.1% O2with a 10 ms integration time are well within the performance required for breath O2monitoring applications.

Gapless tuning of quantum cascade laser frequency combs with external cavity optical feedback.

We present the operation of quantum cascade laser frequency combs in an external cavity configuration. Experimental observations show dependence of comb repetition rate and optical spectrum on the external cavity length. The low phase-noise comb regime is extended to a broader range of bias currents, enabling gapless frequency tuning of the comb modes. Dual-comb measurements also confirm improved comb stability in the presence of unwanted optical feedback when operating in an external cavity configuration. These observations indicate that aside from the continuing efforts to assure low and uniform dispersion characteristics of quantum cascade laser frequency combs, the proposed simple approach of adding a broadband external cavity can significantly enhance operation of sub-optimal devices for spectroscopic applications.

Fugitive methane detection using open-path stand-off chirped laser dispersion spectroscopy.

We report an open-path chirped laser dispersion spectrometer capable of detecting the atmospheric methane concentration above the background using both specular and diffusive reflective surfaces via two distinct operation modes in a stand-off detection configuration. The system is integrated with simultaneous ranging functionality, which enables average concentration measurements for varying optical pathlengths. The system was first tested for accuracy and characterized to achieve sensitivity of 2.9ppm-m/Hz1/2 and pathlength precision of 0.2m/Hz1/2 with a controlled release of methane outside the laboratory. The instrument was subsequently field-deployed in the proximity of a natural gas compressor station for fugitive methane detection. The instrument successfully detected methane plumes and narrowed down the location of the plume through multi-path measurement. The field measurements were verified by a co-located reference mobile methane sensor.

Time-resolved HO2 detection with Faraday rotation spectroscopy in a photolysis reactor.

Faraday rotation spectroscopy (FRS) employs the Faraday effect to detect Zeeman splitting in the presence of a magnetic field. In this article, we present system design and implementation of radical sensing in a photolysis reactor using FRS. High sensitivity (100 ppb) and time resolved in situ HO2 detection is enabled with a digitally balanced acquisition scheme. Specific advantages of employing FRS for sensing in such dynamic environments are examined and rigorously compared to the more established conventional laser absorption spectroscopy (LAS). Experimental results show that FRS enables HO2 detection when LAS is deficient, and FRS compares favorably in terms of precision when LAS is applicable. The immunity of FRS to spectral interferences such as absorption of hydrocarbons and other diamagnetic species absorption and optical fringing are highlighted in comparison to LAS.

Chirped laser dispersion spectroscopy for spectroscopic chemical sensing with simultaneous range detection.

Spectroscopic chemical detection requires knowledge or determination of an optical path for accurate quantification of path-integrated concentration of species. Continuous-wave-laser-based spectroscopic systems operating in an open integrated-path remote sensing configuration are usually not equipped for optical path determination. Here we demonstrate a measurement technique capable of simultaneous spectroscopic chemical quantification and range finding. The range-finding functionality is implemented with chirped laser dispersion spectroscopy. The methodology is potentially useful for remote chemical sensing in a hard-target LIDAR configuration and for automatic calibration of gas cells with unknown or varying lengths.

Dynamic computational optical fringe mitigation in tunable laser absorption spectroscopy.

In optical spectroscopic systems where unwanted optical scattering cannot be eliminated, Fabry-Pérot etalons cause unpredictable changes in the spectral background. Frequent system calibration is then required to maintain the desired measurement accuracy, which presents a major limitation to the spectrometer. We introduce a computational approach to mitigate the adverse effects of optical fringing without hardware modifications. Motivated by experimental observations of complicated fringe behaviors, we simplify the problem by decomposing the fringe background into component etalons that can be addressed according to their individual characteristics. The effectiveness of the proposed method is demonstrated on a silicon photonic methane sensor, where accurate measurements of methane concentration are obtained from spectral data strongly affected by optical fringes.

Adaptive thermal stabilization of an integrated photonic spectrometer using parasitic interference fringes.

Parasitic fringe drift from unwanted scatterings limits the long-term stability of waveguide-based optical spectrometers. Yet their spectral features provide relevant information that can be used to improve performance of the spectrometer. We show that fringe drift can be extracted and utilized to perform accurate thermal stabilization, especially in the case of integrated waveguide sensors. In this Letter, effective stabilization of a methane silicon photonic sensor is demonstrated, and significant reduction in fringe noise is clearly observed.

Computational coherent averaging for free-running dual-comb spectroscopy.

Dual-comb spectroscopy is a rapidly developing spectroscopic technique that does not require any opto-mechanical moving parts and enables broadband and high-resolution measurements with microsecond time resolution. However, for high sensitivity measurements and extended averaging times, high mutual coherence of the comb-sources is essential. To date, most dual-comb systems employ coherent averaging schemes that require additional electro-optical components, which increase system complexity and cost. More recently, computational phase correction approaches that enables coherent averaging of spectra generated by free-running systems have gained increasing interest. Here, we propose such an all-computational solution that is compatible with real-time data acquisition architectures for free-running systems. The efficacy of our coherent averaging algorithm is demonstrated using dual-comb spectrometers based on quantum cascade lasers, interband cascade lasers, mode-locked lasers, and optically-pumped microresonators.

Field Deployment of a Portable Optical Spectrometer for Methane Fugitive Emissions Monitoring on Oil and Gas Well Pads.

We present field deployment results of a portable optical absorption spectrometer for localization and quantification of fugitive methane (CH4) emissions. Our near-infrared sensor targets the 2ν3 R(4) CH4 transition at 6057.1 cm-1 (1651 nm) via line-scanned tunable diode-laser absorption spectroscopy (TDLAS), with Allan deviation analysis yielding a normalized 2.0 ppmv∙Hz-1/2 sensitivity (4.5 × 10-6 Hz-1/2 noise-equivalent absorption) over 5 cm open-path length. Controlled CH4 leak experiments are performed at the METEC CSU engineering facility, where concurrent deployment of our TDLAS and a customized volatile organic compound (VOC) sensor demonstrates good linear correlation (R2 = 0.74) over high-flow (>60 SCFH) CH4 releases spanning 4.4 h. In conjunction with simultaneous wind velocity measurements, the leak angle-of-arrival (AOA) is ascertained via correlation of CH4 concentration and wind angle, demonstrating the efficacy of single-sensor line-of-sight (LOS) determination of leak sources. Source magnitude estimation based on a Gaussian plume model is demonstrated, with good correspondence (R2 = 0.74) between calculated and measured release rates.

Mid-infrared dual-comb spectroscopy with interband cascade lasers.

Two semiconductor optical frequency combs, consuming less than 1 W of electrical power, are used to demonstrate high-sensitivity mid-infrared dual-comb spectroscopy in the important 3-4 µm spectral region. The devices are 4 mm long by 4 µm wide, and each emits 8 mW of average optical power. The spectroscopic sensing performance is demonstrated by measurements of methane and hydrogen chloride with optical multi-pass cell sensitivity enhancement. The system provides a spectral coverage of 33 cm-1 (1 THz), 0.32 cm-1 (9.7 GHz) frequency sampling interval, and peak signal-to-noise ratio of ∼100 at 100 µs integration time. The monolithic design, low drive power, and direct generation of mid-infrared radiation are highly attractive for portable broadband spectroscopic instrumentation in future terrestrial and space applications.

Cavity Attenuated Phase Shift Faraday Rotation Spectroscopy.

Cavity attenuated phase shift Faraday rotation spectroscopy has been developed and demonstrated by oxygen detection near 762 nm. The system incorporates a high-finesse cavity together with phase-sensitive balanced polarimetric detection for sensitivity enhancement and achieves a minimum detectable polarization rotation angle (1σ) of 5.6 × 10-9 rad/√Hz, which corresponds to an absorption sensitivity of 4.5 × 10-10 cm-1/√Hz without the need for high sampling rate data acquisition. The technique is insusceptible to spectral interferences, which makes it highly suitable for chemical trace gas detection of paramagnetic molecules such as nitric oxide, nitrogen dioxide, oxygen, and the hydroxyl/hydroperoxyl radicals.

Frequency-locked cavity ring-down Faraday rotation spectroscopy.

Cavity ring-down Faraday rotation spectroscopy (CRD-FRS) is a technique for trace gas measurements of paramagnetic species that retrieves the molecular concentration from the polarization rotation measured as the difference between simultaneously recorded ring-down times of two orthogonal polarization states. The differential measurement is inherently insensitive to nonabsorber related losses, which makes off-resonance measurements redundant. We exploit this unique property by actively line-locking to a molecular transition for calibration-free trace gas concentration retrieval. In addition, we enhance the effective duty-cycle of the system by implementing a Pound-Drever-Hall laser lock to the cavity resonance, which allows for ring-down rates of up to 9 kHz. The system performance is demonstrated by measurements of trace oxygen with a minimum detection limit at the ppmv/√Hz-level.

Dual-comb spectroscopy using plasmon-enhanced-waveguide dispersion-compensated quantum cascade lasers.

In this Letter, we report on sub-millisecond response time mid-infrared dual-comb spectroscopy using a balanced asymmetric (dispersive) dual-comb setup with a matched pair of plasmon-enhanced-waveguide dispersion-compensated quantum cascade lasers. The system performance is demonstrated by measuring spectra of Bromomethane (CH3Br) and Freon 134a (CH2FCF3) at approximately 7.8 µm. A purely computational phase and timing-correction procedure is used to validate the coherence of the quantum cascade lasers frequency combs and to enable coherent averaging over the time scales investigated. The system achieves a noise-equivalent absorption better than 1×10-3 Hz-1/2, with a resolution of 9.8 GHz (0.326 cm-1) and an optical bandwidth of 1 THz (32 cm-1), with an average optical power of more than 1 mW per spectral element.

Heterodyne interferometric signal retrieval in photoacoustic spectroscopy.

A new heterodyne interferometric method for optical signal detection in photoacoustic or photothermal spectroscopy is demonstrated and characterized. It relies on using one laser beam for the photoacoustic excitation of the gas sample that creates refractive index changes along the beam path, while another laser beam is used to measure these changes. A heterodyne-based detection of path-length changes is presented that does not require the interferometer to be balanced or stabilized, which significantly simplifies the optical design. We discuss advantages of this new approach to photoacoustic signal detection and the new sensing arrangements that it enables. An open-path photoacoustic spectroscopy of carbon dioxide at 2003 nm and a novel sensing configuration that enables three-dimensional spatial gas distribution measurement are experimentally demonstrated.

Optical heterodyne-enhanced chirped laser dispersion spectroscopy.

A proof-of-concept heterodyne-enhanced chirped laser dispersion spectroscopy system is presented. In remote sensing systems where low return powers are expected, the addition of an optical local oscillator and subsequent nonlinear processing can provide improved performance in chirped laser dispersion spectroscopy. Details about the system configuration, phase noise cancellation, and experimental verification are discussed.

Molecular dispersion spectroscopy based on Fabry-Perot quantum cascade lasers.

Two Fabry-Perot quantum cascade lasers are used in a differential dual comb configuration to perform rapidly swept dispersion spectroscopy of low-pressure nitrous oxide with <1 ms acquisition time. Active feedback control of the laser injection current enables simultaneous wavelength modulation of both lasers at kilohertz rates. The system demonstrates similar performance in both absorption and dispersion spectroscopy modes and achieves a noise-equivalent absorption figure of merit in the low 10-4/Hz range.

Wavelength modulated multiheterodyne spectroscopy using Fabry-Pérot quantum cascade lasers.

Multiheterodyne spectroscopy implemented with semiconductor Fabry-Pérot lasers is a method for broadband (> 20 cm-1), high spectral resolution (~1 MHz) and high time resolution (< 1 µs/spectrum) spectroscopy with no moving parts utilizing off-the-shelf laser sources. The laser stabilization approach demonstrated here enables continuous frequency tuning (at 12.5 Hz repetition rate) while allowing for multiheterodyne wavelength modulation spectroscopy (WMS). Spectroscopic detection of N2O around 1185 cm-1 is experimentally realized, which shows a direct absorption sensitivity limit of ~1.5⨯10-3/√Hz fractional absorption per mode. This can be lowered using WMS down to 5⨯10-4/√Hz per mode, limited by optical fringes. This approaches the range of sensitivities of standard single-mode laser based spectrometers, which demonstrates that the multiheterodyne method is well-suited for chemical sensing of spectrally broadened absorption features or for multi-species measurements.