Gas spectroscopy with integrated frequency monitoring, through self-mixing in a terahertz quantum-cascade laser

Terahertz-frequency quantum cascade lasers (THz QCLs) [1] have been used as compact, yet powerful sources of THz radiation in a range of gas spectroscopy techniques [2], including both in situ active sensing [3] and heterodyne radiometry [4]. A novel approach has recently been demonstrated, based on self-mixing interferometry (SMI) in a QCL [5]. This effect occurs when radiation is fed back into the QCL from an external reflector [6]. The resulting interference within the QCL perturbs the terminal voltage, and the absorption spectrum of a gas within the external cavity may be inferred from the amplitude of these perturbations. This eliminates the need for an external THz detector, doubles the interaction-length for absorption spectroscopy, and the scanning speed can potentially be raised to the time-scale of the QCL lasing dynamics (~10 GHz). A limitation reported in the previously published work is that the QCL emission frequency was inferred from prior FTIR measurements of the unperturbed laser. However, the actual system QCL frequency is perturbed by SMI feedback effects and is therefore dependent on the gas absorption crosssection, leading to apparent frequency shifts in the measured spectral lines. In this work, we demonstrate a technique to measure the frequency directly by extending the external cavity length modulation to 200-mm using a motorised linear translation stage [Fig. 1(a)]. The QCL in this system can be tuned by adjusting the drive current, over a 1.5 GHz bandwidth, around a centre frequency of 3.394 THz. Fig. 1(b) shows the transmitted radiation intensity through a 73-cm gas cell with TPX windows, filled with methanol vapour at a pressure of 2 Torr, as a function of drive current, measured using a pyroelectric detector. Two absorption lines are clearly resolved. By replacing the detector with a planar mirror, and recording the QCL voltage modulation as a function of stage position, a full interferogram can be acquired, and a Fourier transform can then be used to determine the laser frequency and the amplitude of the transmitted signal [Fig. 1(c)]. In this paper, we will demonstrate the reconstruction of the methanol absorption spectrum, with direct measurement of the laser frequency using this technique

Detector-free gas spectroscopy, with integrated frequency monitoring, through self-mixing in a terahertz quantum-cascade laser

Terahertz-frequency quantum cascade lasers (THz QCLs) have been used as compact, yet powerful THz radiation sources in a range of gas spectroscopy techniques, including both in situ active sensing and heterodyne radiometry. However, all such approaches require external THz instrumentation (detectors or mixers) in addition to the QCL, thus raising the system complexity and cost. A partial solution has recently been demonstrated, based on self-mixing interferometry (SMI) in a QCL, which occurs when radiation is fed back into the QCL from an external reflector. The resulting interference within the QCL perturbs the terminal voltage, and the absorption spectrum of a gas within the external cavity may be inferred from the amplitude of these perturbations. This both eliminates the need for an external THz detector or mixer, doubles the interaction-length for absorption spectroscopy, and the scanning speed can potentially be raised to the time-scale of the QCL lasing dynamics (~10 GHz). A limitation reported in the previous work is that the QCL emission frequency must be inferred from prior spectral measurements of the unperturbed laser, which introduces two principal problems: (1) additional THz instrumentation is still required, and (2) the system QCL frequency is itself perturbed by feedback effects, leading to apparent frequency shifts in the measured spectral lines. In this work, we demonstrate a technique to measure the QCL frequency directly by extending the external cavity length modulation to 400-mm using a motorised linear translation stage. By recording the QCL voltage modulation as a function of stage position, a full interferogram can be acquired, and a Fourier transform can then be used to determine the laser frequency and the amplitude of the transmitted signal. The QCL was shown to be tunable by adjusting the drive current over a 1.5-GHz bandwidth, around a centre frequency of 3.4052 THz. To demonstrate gas spectroscopy, a 1-m gas cell with TPX windows was filled with methanol vapour, and the transmitted QCL power was measured as a function of drive current through SMI analysis. Two absorption lines are clearly resolved. The technique was found to be accurate to partial methanol pressures of < 10 mTorr. In conclusion, we have demonstrated an accurate and low-cost THz gas spectroscopy technique based on self-mixing in a THz QCL, without the need for any external THz mixer or detector, or a priori calibration of the QCL emission frequency

Direct Measurements of Unimolecular and Bimolecular Reaction Kinetics of the Criegee Intermediate (CH 3 ) 2 COO

The Criegee intermediate acetone oxide, (CH3)2COO, is formed by laser photolysis of 2,2-diiodopropane in the presence of O2 and characterized by synchrotron photoionization mass spectrometry and by cavity ring-down ultraviolet absorption spectroscopy. The rate coefficient of the reaction of the Criegee intermediate with SO2 was measured using photoionization mass spectrometry and pseudo-first-order methods to be (7.3 ± 0.5) × 10–11 cm3 s–1 at 298 K and 4 Torr and (1.5 ± 0.5) × 10–10 cm3 s–1 at 298 K and 10 Torr (He buffer). These values are similar to directly measured rate coefficients of anti-CH3CHOO with SO2, and in good agreement with recent UV absorption measurements. The measurement of this reaction at 293 K and slightly higher pressures (between 10 and 100 Torr) in N2 from cavity ring-down decay of the ultraviolet absorption of (CH3)2COO yielded even larger rate coefficients, in the range (1.84 ± 0.12) × 10–10 to (2.29 ± 0.08) × 10–10 cm3 s–1. Photoionization mass spectrometry measurements with deuterated acetone oxide at 4 Torr show an inverse deuterium kinetic isotope effect, kH/kD = (0.53 ± 0.06), for reactions with SO2, which may be consistent with recent suggestions that the formation of an association complex affects the rate coefficient. The reaction of (CD3)2COO with NO2 has a rate coefficient at 298 K and 4 Torr of (2.1 ± 0.5) × 10–12 cm3 s–1 (measured with photoionization mass spectrometry), again similar to rate for the reaction of anti-CH3CHOO with NO2. Cavity ring-down measurements of the acetone oxide removal without added reagents display a combination of first- and second-order decay kinetics, which can be deconvolved to derive values for both the self-reaction of (CH3)2COO and its unimolecular thermal decay. The inferred unimolecular decay rate coefficient at 293 K, (305 ± 70) s–1, is similar to determinations from ozonolysis. The present measurements confirm the large rate coefficient for reaction of (CH3)2COO with SO2 and the small rate coefficient for its reaction with water. Product measurements of the reactions of (CH3)2COO with NO2 and with SO2 suggest that these reactions may facilitate isomerization to 2-hydroperoxypropene, possibly by subsequent reactions of association products

Release of Spring 2013 Spanish-Language MCAS Test Items

Trace atmospheric concentrations of carboxylic acids have a potent effect upon the environment, where they modulate aqueous chemistry and perturb Earth’s radiative balance. Halogenated carboxylic acids are produced by the tropospheric oxidation of halocarbons and are considered persistent pollutants because of their weak tropospheric and aqueous sinks. However, recent studies reported rapid reactions between selected carboxylic acids and Criegee intermediates, which may provide an efficient gas-phase removal process. Accordingly, absolute rate coefficients of two Criegee intermediates, CH₂OO and (CH₃)₂COO, with a suite of carboxylic acids (HCOOH, CH₃COOH, CClF₂COOH, CF₃CF₂COOH, and pyruvic acid) were measured with a view to develop a structure–activity relationship (SAR). This SAR is based upon the dipole-capture model and predicts the reactivity of many further combinations of Criegee intermediates and carboxylic acids. Complementary synchrotron-based photoionization mass spectrometry measurements demonstrate that these reactions produce stable ester adducts, with a reaction coordinate involving transfer of the acidic hydrogen from the carboxylic acid to the terminal oxygen of the Criegee intermediate. The adduct products are predicted to have low vapor pressures, and coupling of this chemistry with a global atmospheric chemistry and transport model shows significant production of secondary organic aerosol at locations rich in biogenic alkene emissions

Criegee Intermediate–Alcohol Reactions, A Potential Source of Functionalized Hydroperoxides in the Atmosphere

Ozonolysis, the mechanism by which alkenes are oxidized by ozone in the atmosphere, produces a diverse family of oxidants known as Criegee intermediates (CIs). Using a combination of newly acquired laboratory data and global atmospheric chemistry and transport modeling, we find that the reaction of CIs with alcohols, a reaction that was originally employed to trap these reactive species and provide evidence for the ozonolysis mechanism nearly 70 years ago, is occurring in Earth’s atmosphere and may represent a sizable source of functionalized hydroperoxides therein. Rate coefficients are reported for the reactions of CH2OO and (CH3)2COO with methanol and that of CH2OO with ethanol. Substitution about the Criegee intermediate is found to have a strong influence over the reaction rate, whereas substitution on the alcohol moiety does not. Although these reactions are not especially rapid, both the precursors to CIs and alcohols have large emissions from the terrestrial biosphere, leading to a high degree of co-location for this chemistry. We estimate that the products of these reactions, the α-alkoxyalkyl hydroperoxides (AAAHs) have a production rate of ∼30 Gg year–1. To assess the atmospheric lifetime of AAAHs, we used the nuclear ensemble method to construct a UV absorption spectrum from the four lowest energy conformers identified for a representative AAAH, methoxymethyl hydroperoxide. The computed absorption cross-section indicates that these compounds will be lost by solar photolysis, although not so rapidly as to exclude competition from other sinks such as oxidation, thermal decay, and aerosol uptake