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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 NH 3 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 NH 3 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 NH 3 generated in low-pressure nitrogen-hydrogen (N 2 -H 2 ) plasmas., (© 2024. The Author(s).)

Cross-sensitivity limits accurate quantitative detection of species concentrations in all sensor technologies, including laser-based absorption techniques. Absorption sensors capture a signal that combines contributions from all interfering species at a given detection wavelength. Careful selection of the probed spectral line, broadband detection, or upstream separation can partially mitigate cross-sensitivity, however, weak or unidentified signal interference remains a challenge for accuracy. Here, we present a proof-of-principle study to overcome cross-sensitivity by taking advantage of the distinct optical saturation characteristics of different gas mixture components. By controlling the absorption contribution of a selected species by intentional optical saturation, simultaneous and quantitative detection of two interfering species becomes possible even without the need for spectral scanning, hence offering two species-one wavelength detection (2S1W) capability. Demonstrated with direct absorption and cavity-ringdown setups, the method offers a new, previously unexploited opportunity to further enhance laser-based analyzers for complex gas mixture analysis in environmental, medical, and technical applications., (© 2023. Springer Nature Limited.)

Brominated organic compounds are toxic ocean-derived trace gases that affect the oxidation capacity of the atmosphere and contribute to its bromine burden. Quantitative spectroscopic detection of these gases is limited by the lack of accurate absorption cross-section data as well as rigorous spectroscopic models. This work presents measurements of high-resolution spectra of dibromomethane, CH 2 Br 2 , from 2960 cm -1 to 3120 cm -1 by two optical frequency comb-based methods, Fourier transform spectroscopy and a spatially dispersive method based on a virtually imaged phased array. The integrated absorption cross-sections measured using the two spectrometers are in excellent agreement with each other within 4%. A revisited rovibrational assignment of the measured spectra is introduced, in which the progressions of features are attributed to hot bands rather than different isotopologues as was previously done. Overall, twelve vibrational transitions, four for each of the three isotopologues CH 2 81 Br 2 , CH 2 79 Br 81 Br, and CH 2 79 Br 2 , are assigned. These four vibrational transitions are attributed to the fundamental ν 6 band and the nearby nν 4 + ν 6 - nν 4 hot bands (with n = 1-3) due to the population of the low-lying ν 4 mode of the Br-C-Br bending vibration at room temperature. The new simulations show very good agreement in intensities with the experiment as predicted by the Boltzmann distribution factor. The spectra of the fundamental and the hot bands show progressions of strong Q K a ( J ) rovibrational sub-clusters. The band heads of these sub-clusters are assigned and fitted to the measured spectra, providing accurate band origins and the rotational constants for the twelve states with an average error of 0.0084 cm -1 . A detailed fit of the ν 6 band of the CH 2 79 Br 81 Br isotopologue is commenced after assigning 1808 partially resolved rovibrational lines, with the band origin, rotational, and centrifugal constants as fit parameters, resulting in an average error of 0.0011 cm -1 .

Bromoacetaldehyde (BrCH 2 CHO) is a major stable brominated organic intermediate of the bromine-ethylene addition reaction during the arctic bromine explosion events. Similar to acetaldehyde, which has been recently identified as a source of organic acids in the troposphere, it may be subjected to photo-tautomerization initially forming brominated vinyl compounds. In this study, we investigate the unimolecular reactions of BrCH 2 CHO under both photolytic and thermal conditions using high-level quantum chemical calculations and Rice-Ramsperger-Kassel-Marcus (RRKM)/master equation analysis. The unimolecular decomposition of BrCH 2 CHO takes place through 14 dissociation and isomerization channels along a potential energy surface involving eight wells. Under the assumption of singlet ground-state potential energy surface-dominated photodynamics, the primary photodissociation yields of BrCH 2 CHO are investigated under both collision-free and collision energy transfer conditions. At atmospheric pressure and under tropospheric actinic flux conditions at ground level, depending on the assumed collisional energy transfer parameter, 150 cm -1 < ⟨Δ E down ⟩ < 450 cm -1 , 78-33% of BrCH 2 CHO undergoes direct photodissociation instead of collisional deactivation at an excitation wavelength of 320 nm. This is significantly higher than the 14% reported for acetaldehyde, hence indicating a strong effect of bromine substitution on the product photolysis yield that is related to additional favorable Br and HBr forming dissociation channels. In contrast to the overall photodissociation quantum yield, the relative branching fractions of the photodissociation products are less dependent on the collisional energy transfer parameter. For a representative value of ⟨Δ E down ⟩ = 300 cm -1 and an excitation wavelength of 320 nm, with 27% for C-C bond fission, 11% for C-Br bond fission, 7% for HBr elimination, and only below 2% each for a consecutive O-Br fission reaction and the photo-tautomerization channel yielding brominated vinyl alcohol, the photodissociation is markedly different from the acetaldehyde case. Finally, as brominated halogenated compounds are of interest for flame inhibition purposes, thermal multichannel unimolecular rate constants were calculated for temperatures in the range from 500 to 2000 K. At a temperature of 2000 K and ambient pressure, the two main reaction channels are the C-Br and C-C bond fissions, contributing 35 and 43% to the total reaction flux, respectively.

We report the first photoacoustic detection scheme using an optical frequency comb-optical frequency comb photoacoustic spectroscopy (OFC-PAS). OFC-PAS combines the broad spectral coverage and the high resolution of OFCs with the small sample volume of cantilever-enhanced PA detection. In OFC-PAS, a Fourier transform spectrometer (FTS) is used to modulate the intensity of the exciting comb source at a frequency determined by its scanning speed. One of the FTS outputs is directed to the PA cell and the other is measured simultaneously with a photodiode and used to normalize the PA signal. The cantilever-enhanced PA detector operates in a non-resonant mode, enabling detection of a broadband frequency response. The broadband and the high-resolution capabilities of OFC-PAS are demonstrated by measuring the rovibrational spectra of the fundamental C-H stretch band of CH4, with no instrumental line shape distortions, at total pressures of 1000 mbar, 650 mbar, and 400 mbar. In this first demonstration, a spectral resolution two orders of magnitude better than previously reported with broadband PAS is obtained, limited by the pressure broadening. A limit of detection of 0.8 ppm of methane in N2 is accomplished in a single interferogram measurement (200 s measurement time, 1000 MHz spectral resolution, 1000 mbar total pressure) for an exciting power spectral density of 42 μW/cm-1. A normalized noise equivalent absorption of 8 × 10-10 W cm-1 Hz-1/2 is obtained, which is only a factor of three higher than the best reported with PAS based on continuous wave lasers. A wide dynamic range of up to four orders of magnitude and a very good linearity (limited by the Beer-Lambert law) over two orders of magnitude are realized. OFC-PAS extends the capability of optical sensors for multispecies trace gas analysis in small sample volumes with high resolution and selectivity.

Methyl iodide is a toxic halocarbon with diverse industrial and agricultural applications, and it is an important ocean-derived trace gas that contributes to the iodine burden of the atmosphere. Quantitative analysis of CH 3 I is mostly based on gas chromatography coupled with mass spectrometry or electron capture detection (GC-MS/ECD) as of yet, which often limits the ability to conduct in situ high-frequency monitoring studies. This work presents an alternative detection scheme based on mid-infrared continuous wave cavity ringdown spectroscopy (mid-IR cw-CRDS). CH 3 I was detected at the R R 2 (15) rovibrational absorption transition at ṽ = 3090.4289 cm -1 ; part of the corresponding v 4 vibration band has been measured with Doppler-limited resolution for the first time. A line strength of S(T = 295 K) = (545 ± 20) cm/mol, corresponding to a line center absorption cross-section σ c (p = 0 bar) = (1.60 ± 0.06) × 10 5 cm 2 /mol, and pressure-broadening coefficients γ p (Ar) = (0.094 ± 0.002) cm -1 /bar and γ p (N 2 ) = (0.112 ± 0.003) cm -1 /bar have been determined. The performance of the detection system has been demonstrated with a tank-purging experiment and has been directly compared with a conventional GC-MS/ECD detection system. Quantitative detection with high reproducibility and continuous sampling is possible with a current noise-equivalent limit of detection of 15 ppb at 20 mbar absorption-cell pressure and 70 s averaging time. This limit of detection is suitable for practical applications in the ppm mixing ratio level range such as workplace monitoring, leak detection, and process studies. Natural environmental abundances are much lower, therefore possibilities for future improvement of the detection limit are discussed.

The Doppler limited non-saturated rotationally resolved infrared spectra of the symmetric and asymmetric CH-stretch bands of CH 2 Br 2 have been measured. A continuous wave cavity ringdown setup with a widely tunable Mid-IR-OPO laser light source yielded a single-shot minimum absorption of 4.9×10 -8 cm -1 . In contrast to the heavily congested ν 1 band, the ν 6 band showed partially resolved rotational features that may serve as suitable absorption targets in future environmental detection schemes for CH 2 Br 2 . A straightforward, VPT2 (second-order vibrational perturbation theory) assisted quantum-chemical approach for assigning the rotational structure has been tested using different model chemistries. The molecular structures, anharmonic frequencies and the structural changes upon vibrational excitation of CH 2 Br 2 have been investigated. The predicted changes of the anharmonic rotational constants have been used together with available spectroscopic ground state constants to simulate the rovibrational structures of the ν 1 and ν 6 bands of CH 2 Br 2 . A refined analysis of the ν 6 band is presented yielding accurate values for the band origin and the rotational constants. A fit of the line positions of 312 prominent transitions of the three isotopologues revealed a low standard error of 0.00056cm -1 , hence within the absolute 0.0009cm -1 wavelength accuracy of the used spectrometer setup. A combined analysis of the predicted line strengths and positions of the strong Q sub-branches of the ν 6 band has been performed to test the ability of the different density functionals for VPT2 prediction of anharmonic molecular constants. The M06/6-311++G(d,p) model chemistry turned out to yield reliable state-dependent rotational constants that are accurate enough to reproduce the overall rotational structure even without fitting., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Cavity ringdown spectroscopy (CRDS) in the linear absorption regime is a well-established method for sensitive trace gas detection, but only a few studies have addressed quantitative measurements in the presence of a saturated sample. In fact, saturation is usually avoided in order to escape from the required complex modeling of the saturation process that depends on the characteristics of the absorbing species, its interaction with the surrounding gas as well as on the temporal and spectral characteristics of the cavity excitation. Conversely, the novel saturated-absorption cavity ringdown spectroscopy approach (SCAR/Sat-CRDS) takes advantage of sample saturation in order to allow one to extract both the gas absorption and the empty cavity loss rates from a single ringdown event. Using a new continuous-wave infrared CRD spectrometer equipped with a tunable narrow-bandwidth high-power OPO laser system and a 18 bit digitizer, the transient dynamics of absorption saturation and the working limits of the Sat-CRDS approach in terms of its ability to extract reliable trace gas concentrations have been experimentally studied in this work. Using a strong methane transition as a test case, the excitation power P0 and saturation power PS have been systematically varied to explore a wide range of saturation regimes. At pressures 5 μbar < p < 2 mbar, the saturation intensity revealed a nearly linear pressure dependence showing that non-collisional processes contribute to the overall relaxation. A ratio of P0/PS ≈ 15 turned out to be optimal with working limits of 5 < P0/PS < 300. Moreover, the ratio of the absorption and empty cavity loss rates, γg/γc, has been varied to test the dynamic range of the method. At γg > γc, a pronounced coupling between the two parameters has been observed. Finally, a standard error analysis was performed revealing that the Sat-CRDS approach holds its advantages over conventional CRDS implementations in particular when the attainable ultimate detection sensitivity is limited by uncertainties in the empty cavity ringdown constant.