Measurements of nitrogen-broadening coefficients in the ν3 band of the hydroperoxyl radical using a continuous wave quantum cascade laser

Mid-infrared absorption spectroscopy was applied to the detection of the hydroperoxyl radical (HO₂) in pulsed laser photolysis combined with a laser absorption kinetics reactor. The transition of the ν₃ vibrational band assigned to the O-O stretch mode around 1065 cm⁻¹ was probed with a thermoelectrically cooled, continuous wave, mid-infrared, distributed feedback quantum cascade laser (QCL). The HO₂ was generated through 355 nm photolysis of Cl₂/1,4-c-C₆H₈/O₂ mixtures. The mid-infrared absorption spectrum of the HO₂ radical was recorded between 1064 and 1065.5 cm⁻¹. The absorption line shapes were well represented by the Voigt profile. The nitrogen-broadening coefficients of the HO₂ radical at 295 K were determined for four absorption lines around 1065 cm⁻¹. Mid-infrared absorption detection using a QCL as a spectroscopic light source is a powerful method in spectroscopic and kinetics studies of the HO₂ radical.     

On the direct formation of HO2 radicals after 248 nm irradiation of benzene C6H6 in the presence of O2

We present in this work the direct observation of HO₂ radicals after irradiation of benzene C₆H₆ at 248 nm in the presence of O₂. HO₂ radicals have been unambiguously identified using the very selective and sensitive detection of continuous wave cavity ring-down spectroscopy (cw-CRDS) coupled to a laser photolysis reactor. HO₂ radicals were detected in the first vibrational overtone of the OH stretch at 6638.20 cm^-1, using a DFB diode laser. This reaction might be important because 248 nm photolysis of H₂O₂ has often been used in the past for studying the OH^•-initiated degradation of C₆H₆, often using a large excess of C₆H₆ over H₂O₂. The possible importance of the title reaction with respect to these former laboratory studies has been quantified through comparison with HO₂ ^• signals obtained from 248 nm photolysis of H₂O₂: one obtains under our conditions (excess O₂ and total pressure of 6.6 kPa helium) from the 248 nm irradiation of identical initial concentrations [C₆H₆]=[H₂O₂] the following relative initial radical concentrations: [HO₂ ^•]=(0.28±0.05)×[OH^•]. Experiments with various O₂ concentrations have revealed that the origin of the HO₂ radicals is not the reaction of H-atoms with O₂, but must originate from the reaction of O₂ with excited C₆H₆ ^*. The quantum yield of C₆H₆ ^* formation has been deduced to ϕ=0.2±0.1. PACS  42.62.Fi; 82.20.Pm; 82.33.Tb     

A study of OH radicals in an atmospheric AC discharge plasma using near infrared diode laser cavity ringdown spectroscopy combined with optical emission spectroscopy

Simultaneous measurements of absolute concentrations of H₂O and OH radicals in an atmospheric AC discharge using continuous wave cavity ringdown spectroscopy (cw-CRDS) are reported. Formation of OH radicals and plasma temperatures are characterized by optical emission spectroscopy. The concentration of OH radical at the edge of the discharge plume at 380 K is measured by the cw-CRDS technique to be 1.1 ×10¹⁵ molecule cm^-3. Ringdown measurements of the H₂O (120-000) band and the OH first overtone around 1515 nm enable us to determine an OH generation yield, , to be 4.8 ×10^-3, where N_OH and are the number densities of OH and H₂O, respectively. The minimum detectable absorption coefficient of the cw-CRDS system is 8.9 ×10^-9  cm^-1, which corresponds to a 1σ detection limit of OH number density of 1.2 ×10¹³ molecule cm^-3 in the discharge. This experimental approach is demonstrated for the first time ever in an AC discharge, and can be applied in general to a variety of atmospheric plasmas to help study OH formation mechanisms and OH-related plasma applications.     

Quantum chemical studies of the OH-initiated oxidation reactions of propenols in the presence of O2

ABSTRACT

The atmospheric oxidation mechanisms of 1- and 2-propenol initiated by OH radical have been theoretically investigated at the CCSD(T)//BH&;HLYP/6-311?+?+G(d,p) level of theory. Conventional transition state theory was employed to predict the rate constants for the initial reaction channels. The calculations clearly indicate that OH-addition channels contribute maximum to the total reaction, both for 1- and 2-propenol, while H-abstraction channels can be neglected at the temperature range of 220–520?K. The calculated total rate constants at 298?K are 1.66?×?10^?11 and 7.69?×?10^?12 cm³?molecule^?1?s^?1 respectively for 1- and 2-propenol, which are in reasonable agreement with the experimental values of similar systems (vinyl ethers?+?OH reactions). The deduced Arrhenius expressions are k(OH?+?1-propenol)?=?1.43?×?10^?12 exp[(743.7?K)/T] and k(OH?+?2-propenol)?=?2.86?×?10^?12 exp[(310.5?K)/T] cm³?molecule^?1?s^?1. Under atmospheric condition, the OH-addition intermediates (CH₃C?HCH(OH)₂, CH₃CH(OH)C?H(OH), CH₃CH(OH)₂?CH₂, CH₃?C(OH)CH₂(OH)) are likely to react rapidly with O₂, the theoretically identified major products for 1-propenol are HCOOH, CH₃CHO and CH₃CH(OH)CHO, and the dominant products for 2-propenol are CH₃COOH, HCHO and CH₃COCH₂OH, both companied with the regeneration of OH and HO₂ radicals (crucial reactive radicals in the atmosphere).     

Air-broadening coefficients of the HO2 radical in the 2ν1 band measured using cw-CRDS

In this paper we present measurements of the air-broadening coefficients of HO₂ at room temperature in the 2ν₁ band around 1.5 microns. The HO₂ radicals were created by flash photolysis of SOCl₂ in a flow of O₂/CH₃OH mixtures. To observe air-broadening, N₂ (79%) and O₂ (21%) were added using calibrated flow controllers and a total pressure controller. The total pressure was monitored in parallel using a capacitive pressure gauge. Air-broadening coefficients at 296 K were determined for 34 absorption lines between 6631 and 6671 cm⁻¹. The air-broadening coefficients of HO₂ show a rotational dependence (decreasing from about 0.14 cm⁻¹/atm for N″ = 3 to about 0.09 cm⁻¹/atm for N″ = 10). No evidence for collisional narrowing was observed.     

Sensitive absorption measurements in the near-infrared region using off-axis integrated-cavity-output spectroscopy

A novel instrument that employs a high-finesse optical cavity as an absorption cell has been developed for sensitive measurements of gas mixing ratios using near-infrared diode lasers and absorption-spectroscopy techniques. The instrument employs an off-axis trajectory of the laser beam through the cell to yield an effective optical path length of several kilometers without significant unwanted effects due to cavity resonances. As a result, a minimum detectable absorption of approximately 1.4×10^-5 over an effective optical path of 4.2 km was obtained in a 1.1-Hz detection bandwidth to yield a detection sensitivity of approximately 3.1×10^-11 cm^-1 Hz^-1/2. The instrument has been used for sensitive measurements of CO, CH₄, C₂H₂ and NH₃. Received: 6 May 2002 / Revised version: 31 May 2002 / Published online: 2 September 2002 RID="*" ID="*"Corresponding author. Fax: +1-650/965-7074, E-mail: d.baer@lgrinc.com     

Spectroscopy of the excited C-O stretching Q branch of 13CD3OH: Measurement and assignment of new FIR laser lines

The Q branch of the C-O stretching fundamental band of ¹³CD₃OH has been investigated. Starting from a high resolution (4 × 10⁻³cm⁻¹) infrared Fourier transform spectrum and using a waveguide CO₂ laser of 300 MHz tunability and an acoustooptic modulator for an extension of ±90 MHz, 31 new FIR laser lines have been observed. The related absorptions have been measured by means of optoacoustic detection. The frequency of one new FIR laser line was also measured. Eight tentative assignments are proposed for the IR absorption and FIR laser emissions.     

Measurement of the absolute Raman scattering cross sections of sulfur and the standoff Raman detection of a 6‐mm‐thick sulfur specimen at 1500 m

The absolute Raman scattering cross sections (σ_RS) for the 471, 217, and 153 cm⁻¹ modes of sulfur were measured as 6.0 ± 1.2 × 10⁻²⁷, 7.7 ± 1.6 × 10⁻²⁷, and 1.2 ± 0.24 × 10⁻²⁶ cm² at 815, 799, and 794 nm, respectively, using a 785‐nm pump laser. The corresponding values of σ_RS at 1120, 1089, and 1081 nm were determined to be 1.5 ± 0.3 × 10⁻²⁷, 1.2 ± 0.24 × 10⁻²⁷, and 1.2 ± 0.24 × 10⁻²⁷ cm² using a 1064‐nm laser. A temperature‐controlled, small‐cavity (2.125 mm diameter) blackbody source was used to calibrate the signal output of the Raman spectrometers for these measurements. Standoff Raman detection of a 6‐mm‐thick sulfur specimen located at 1500 m from the pump laser and the Raman spectrometer was made using a 1.4‐W, CW, 785‐nm pump laser. Copyright © 2010 John Wiley & Sons, Ltd.     

Quantum chemical study of the (Z)-2-penten-1-ol (HOCH2–CH = CHCH2CH3) + OH + O2 reactions

ABSTRACT

The mechanism and products of the reaction of (Z)-2-penten-1-ol [(Z)-PO21] with OH radical in the presence of O₂ have been elucidated by using high-level quantum chemical methods CCSD(T)/6-311+G(d,p)//BH&;HLYP/6-311++G(d,p). The calculations clearly indicate that addition channels contribute maximum to the total reaction and H-abstraction channels can be neglected at temperatures of 220–500 K. The rate constant for the reaction of OH radical with (Z)-PO21 at 298 K is computed to be 1.22 × 10^?10 cm³ molecule^?1 s^?1, which is in stronger agreement with the previously reported experimental values. The kinetic data obtained over the temperature range 220?500 K are used to derive an non-Arrhenius expression: k = 3.69 × 10^?13 × exp(1763.7/T) cm³ molecule^?1 s^?1. For the reaction of (Z)-PO21with OH radical in the presence of O₂, the major primary reaction products found in this study are propanal [CH₃CH₂C(O)H] and glycolaldehyde [HOCH₂C(O)H], whereas formaldehyde [HC(O)H], 2-hydroxybutanal [CH₃CH₂CH(OH)C(O)H] and the epoxide P18 are anticipated to be minor products. The calculated results are consistent with the recent experimental observations.     

Off-axis continuous-wave cavity-enhanced absorption spectroscopy of narrow-band and broadband absorbers using red diode lasers

We present an application of continuous-wave (cw) cavity-enhanced absorption spectroscopy (CEAS) with off-axis alignment geometry of the cavity and with time integration of the cavity output intensity for detection of narrow-band and broadband absorbers using single-mode red diode lasers at λ=687.1 nm and λ=662 nm, respectively. Off-axis cw CEAS was applied to kinetic studies of the nitrate radical using a broadband absorption line at λ=662 nm. A rate constant for the reaction between the nitrate radical and E-but-2-eneof (3.78±0.17)×10^-13 cm³ molecule^-1 s^-1 was measured using a discharge-flow system. A nitrate-radical noise-equivalent (1σ≡ root-mean-square variation of the signal) detection sensitivity of 5.5×10⁹ molecule cm^-3 was achieved in a flow tube with a diameter of 4 cm and for a mirror reflectivity of ∼99.9% and a lock-in amplifier time constant of 3 s. In this case, a noise-equivalent fractional absorption per one optical pass of 1.6×10^-6 was demonstrated at a detection bandwidth of 1 Hz. A wavelength-modulation technique (modulation frequency of 10 kHz) in conjunction with off-axis cw CEAS has also been used for recording 1f- and 2f-harmonic spectra of the ^RR(15) absorption of the b¹Σ_g ⁺-X³Σ_g ^- (1,0) band of molecular oxygen at =14553.947 cm^-1. Noise-equivalent fractional absorptions per one optical pass of 1.35×10^-5, 6.9×10^-7 and 1.9×10^-6 were obtained for direct detection of the time-integrated cavity output intensity, 1f- and 2f-harmonic detection, respectively, with a mirror reflectivity of ∼99.8%, a cavity length of 0.22 m and a detection bandwidth of 1 Hz. Received: 24 June 2002 / Revised version: 12 August 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +44-1865/275410, E-mail: vlk@physchem.ox.ac.uk     

Wavenumber measurement of weak CO2 laser lines around 10.6 μm

An experimental method is described in which a tunable semiconductor diode laser and the regular CO₂ laser lines are utilized to measure the wavenumber of CO₂ laser lines to an accuracy of about ±5 × 10^?4 cm^?1. Twenty new CO₂ laser lines have been measured over the 943 to 951 cm^?1 region.     

Determination of the OH radical in atmospheric pressure dielectric barrier discharge plasmas using near infrared cavity ring-down spectroscopy

The hydroxyl radical (OH) plays an important role in combustion systems, atmospheric chemistry and the removal of air pollutants by non-thermal plasmas. The present work reports the determination of the hydroxyl radicals in atmospheric dielectric barrier discharge plasmas via near infrared continuous wave cavity ring-down spectroscopy. The P-branches of OH X²Π_i (ν' = 2 ←ν^′′ = 0) bands were used for its number density measurements. The minimum measurable absorption coefficient is about 3 × 10^-8 cm^-1 in DBD plasmas. At certain experimental conditions (a.c. frequency of 70 kHz, 6700 ppm H₂O in He, 1 atm), when the peak-to-peak discharge voltage varied from 6 kV to 10.4 kV, the determined OH radical concentration increased from (2.1 ± 0.1) × 10¹³ molecules cm^-3 to (3.7 ± 0.1) × 10¹³ molecules cm^-3. The plasma gas temperature, derived from the Boltzmann plots of OH rotational population distributions, ranged from 312 ± 10 K to 363 ± 10 K when the discharge voltage was raised in the above range. The influences of O₂ and N₂ addition on the production of OH radicals have been also investigated.     

Carbon dioxide and ammonia detection using 2 μm diode laser based quartz-enhanced photoacoustic spectroscopy

Quartz-enhanced photoacoustic spectroscopy was employed for trace gas concentration measurements of CO₂ and NH₃ using a continuous wave thermoelectrically cooled, distributed feedback diode laser operating at 2 μm. A normalized noise equivalent absorption coefficient, NNEA(1σ)=1.4×10^-8 cm^-1W/ was obtained for CO₂ using the R18 line of the 2ν₁+ν₃ band at 4991.26 cm^-1. This corresponds to minimum detection limit (1σ) of 18 parts per million (ppm) for a 1 s lock-in time constant. The influence of the H₂O presence in the sample gas mixture on the CO₂ sensor performance was investigated. Ammonia detection was performed using the ^P P ₆(6)_S line of the ν₃+ν₄ band at 4986.99 cm^-1. A detection limit (1σ) of 3 ppm for NH₃ concentration with a 1 s lock-in time constant was achieved. This results in a normalized noise equivalent absorption of NNEA(1σ)=8.9×10^-9 cm^-1W/. PACS 82.80.Kq; 46.62.Fi; 42.55.Px     

QEPAS methane sensor performance for humidified gases

A trace gas sensor based on quartz enhanced photoacoustic spectroscopy (QEPAS) was evaluated using humidified nitrogen samples and ambient air. Relaxation processes following vibrational excitation of 2ν₃ state of CH₄ were investigated. Sensor performance at different gas pressures could be predicted based on a developed kinetic model. The experimentally determined normalized detection sensitivity for CH₄ in humid gas is 1.0×10^-8 cm^-1 W/Hz^1/2. PACS  82.80.Kq; 42.62.Fi     

Use of cw-CRDS for studying the atmospheric oxidation of acetic acid in a simulation chamber

The coupling between cavity ring-down spectroscopy (CRDS) and an environmental chamber in the investigation of photo-induced reaction mechanisms is demonstrated for the first time. The development of the CRDS device and the corresponding analytical performances are presented. The first application is devoted to the investigation of the branching ratio of the ^?OH radical reaction of CH₃C(O)OH and CH₃C(O)OD under tropospheric conditions. An environmental chamber coupled to two complementary detection systems is used:

gas chromatography with FTIR spectroscopy for quantitative detection of acetic acid;

CRDS for quantitative detection of CO₂.

Investigation of the reaction kinetics of ^?OH+CH₃C(O)OH gives a rate constant of (6.5±0.5)×10^-13 cm³?molecule^-1?s^-1 (296 K) and shows good agreement with literature data. The product study indicates that the H-abstraction channel from the acid group is the dominant pathway with a branching ratio of (78±13)%, whereas the corresponding D-abstraction channel in the ^?OH+CH₃C(O)OD reaction represents only (36±7)%. This result could be attributed to a strong kinetic isotope effect. Glyoxylic acid has also been detected for the first time as by-product. These results illustrate the high interest of the CRDS technique in the investigation of atmospheric relevant problems.     

Measurement of the absolute Raman scattering cross section of the 1584‐cm−1 band of benzenethiol and the surface‐enhanced Raman scattering cross section enhancement factor for femtosecond laser‐nanostructured substrates

The absolute Raman scattering cross section (σ_RS) for the 1584‐cm⁻¹ band of benzenethiol at 897 nm (1.383 eV) has been measured to be 8.9 ± 1.8 × 10⁻³⁰ cm² using a 785‐nm pump laser. A temperature‐controlled, small‐cavity blackbody source was used to calibrate the signal output of the Raman spectrometer. We also measured the absolute surface‐enhanced Raman scattering cross section (σ_SERS) of benzenethiol adsorbed onto a silver‐coated, femtosecond laser‐nanostructured substrate. Using the measured values of 8.9 ± 1.8 × 10⁻³⁰ and 6.6 ± 1.3 × 10⁻²⁴ cm² for σ_RS and σ_SERS respectively, we calculate an average cross‐section enhancement factor (EF) of 0.8 ± 0.3 × 10⁶. Copyright © 2009 John Wiley & Sons, Ltd.     

Optical-feedback cavity-enhanced absorption spectroscopy with a quantum-cascade laser yields the lowest formaldehyde detection limit

We report on the first application of Optical Feedback-Cavity Enhanced Absorption Spectroscopy to formaldehyde trace gas analysis at mid-infrared wavelengths. A continuous-wave room-temperature, distributed-feedback quantum cascade laser emitting around 1,769 cm^?1 has been successfully coupled to an optical cavity with finesse 10,000 in an OF-CEAS spectrometer operating on the ν₂ fundamental absorption band of formaldehyde. This compact setup (easily transportable) is able to monitor H₂CO at ambient concentrations within few seconds, presently limited by the sample exchange rate. The minimum detectable absorption is 1.6 × 10^?9 cm^?1 for a single laser scan (100 ms, 100 data points), with a detectable H₂CO mixing ratio of 60 pptv at 10 Hz. The corresponding detection limit at 1 Hz is 5 × 10^?10 cm^?1, with a normalized figure of merit of 5 × 10^?11cm $^{-1}/\sqrt{\rm Hz}$ (100 data points recorded in each spectrum taken at 10 Hz rate). A preliminary Allan variance analysis shows white noise averaging down to a minimum detection limit of 5 pptv at an optimal integration time of 10 s, which is significantly better than previous results based on multi-pass or cavity-enhanced tunable QCL absorption spectroscopy.     

钴离子注入对二氧化钛晶体的结构和光学性能的影响

采用离子注入法制备了钴离子掺杂的金红石相TiO₂样品;离子注入能量、注量分别为40 keV(1×10¹⁶cm^-2),80 keV(5×10¹⁵,1×10¹⁶,5×10¹⁶,1×10¹⁷cm^-2),120 keV(1×10¹⁶cm^-2). 通过XRD,XPS和UV-Vis等手段对掺杂前后样品的结构和光学性能进行了表征,分析了掺杂元素在金红石TiO₂中的存在形式. XRD测试表明随着注入能量的增加晶体的损伤程度增加. UV-Vis测试表明掺杂后所有样品在可见光区的吸收增强; 并且随着注量的增加,注量为5×10¹⁵cm^-2到5×10¹⁶cm^-2范围内注入样品的光学带隙逐渐变小. 关键词： 钴 二氧化钛 离子注入 掺杂     

Detection of C2H2 and HCl using mid-infrared degenerate four-wave mixing with stable beam alignment: towards practical in situ sensing of trace molecular species

A stable and convenient optical system to realize the forward phase-matching geometry for degenerate four-wave mixing (DFWM) is demonstrated in the mid-infrared spectral region by measuring DFWM signals generated in acetylene (C₂H₂) and hydrogen chloride (HCl) molecules by probing the fundamental ro-vibrational transitions. IR laser pulses tunable from 2900 cm^?1 to 3350 cm^?1 with a 0.025 cm^?1 linewidth were obtained using a laser system composed of an injection seeded Nd:YAG laser, a dye laser, and a frequency mixing unit. At room temperature and atmospheric pressure, a detection limit of 35 ppm (～ 9.5×10¹⁴ molecules/cm³) for C₂H₂ was achieved in a gas flow of a C₂H₂/N₂ mixture by scanning the P(11) line of the (010(11)⁰)–(0000⁰0⁰) band. The detection limit of the HCl molecule was measured to be 25 ppm (～6.8×10¹⁴ molecules/cm³) in the same environment by probing the R(4) line. The dependences of signal intensities on molecular concentrations and laser pulse energies were demonstrated using C₂H₂ as the target species. The variations of the signal line shapes with changes in the buffer gas pressures and laser intensities were recorded and analyzed. The experimental setup demonstrated in this work facilitates the practical implementation of in situ, sensitive molecular species sensing with species-specific, spatial and temporal resolution in the spectral region of 2.7–3.3 μm (3000–3700 in cm^?1), where various molecular species important in combustion have absorption bands.     

Photo-acoustic and photo-refractive detection of small absorptions in liquids

The sensitivities of pulsed photo-acoustic and photo-refractive (e.g., thermal lensing) techniques for the measurement of small absorptions in liquids have been evaluated both theoretically and experimentally. Electrostriction limits the sensitivity of both techniques, this limitation is less severe for the photo-refractive technique. The minimum absorption constants observed experimentally, for a 200-μm laser spot size in liquid N₂, are 4 × 10^-5 cm^-1 for the photo-acoustic measurement and 6 × 10^-7 cm^-1 for the photo-refractive measurement. The calculated electrostrictive limits are 2 × 10^-5 cm^-1 and 7 × 10^-11 cm^-1, respectively.