A diode laser system for long-path,automatic monitoring of SO2

A diode laser system for automatic monitoring of SO₂ along a 60 m atmospheric path is reported. The laser is wavelength modulated and is used to obtain i.r. absorption spectra from the measurement path. These spectra are automatically correlated with reference spectra obtained simultaneously from a calibration cell. The minimum detectable SO₂ concentration is at present around 100 ppb.     

Spectroscopic trace-gas sensor with rapidly scanned wavelengths of a pulsed quantum cascade laser for in situ NO monitoring of industrial exhaust systems

Development of a pulsed quantum cascade laser (QCL)-based spectroscopic trace-gas sensor for sub-part-per-million detection of nitric oxide (NO) and capable of monitoring other molecular species such as CO₂, H₂O, and NH₃ in industrial combustion exhaust systems is reported. Rapid frequency modulation is applied to the QCL to minimize the influence of fluctuating non-selective absorption. A novel method utilizes only a few laser pulses within a single wavelength scan to probe an absorption spectrum at precisely selected optical frequencies. A high-temperature gas cell was used for laboratory evaluation of the NO sensor performance. A noise-equivalent sensitivity (1) of 100 ppb × m/ at room temperature and 200 ppb × m/ at 630 K was achieved by measuring the NO R(6.5) absorption doublet at 1900.075 cm^–1.     

A PbSe diode laser spectrometer to be used in air pollution monitoring and mineral prospecting

A high resolution infra-red PbSe diode laser spectrometer has been developed for application in air pollution monitoring and mineral prospecting. This instrument possesses three cells for measurement and calibration. Correlation techniques have been applied to increase the sensitivity. SO₂ concentrations of around 5 ppm have been monitored at 7.3m with the diode operating at 77 K.     

Selective optothermal detection of NO2 and H2O with a frequency-tuned CO waveguide laser

The results are reported of the CO-laser optothermal (OT) detection of impurity gases when their absorption spectra overlap with those of an interfering gas. The influence of the latter was avoided using low gas pressures corresponding to a maximum of the OT sensitivity. Frequency tuned in the 5.2–6.3 m wavelength range, ¹²C¹⁶O and ¹³C¹⁶O waveguide lasers were used. The fine frequency tuning at 490 MHz was achieved for 150 laser transitions of both molecules. The OT sensitivity was estimated by NO₂ detection in the presence of water vapor. The minimal detectable concentration proved to be 60 ppb at P _19–18(14) transition of a ¹²C¹⁶O laser for NO₂ and 75 ppb on P _12–11(13) transition of a ¹³C¹⁶O laser for H₂O.     

Measurement of tropospheric O3, SO2 and aerosol from a volcanic emission event using new multi-wavelength differential-absorption lidar techniques

We present measurements of tropospheric O₃, SO₂ and aerosol from a volcanic emission event using new multi-wavelength differential absorption lidar (DIAL) techniques that enable us to remove the mutual effects between O₃ and SO₂ from the raw measurements. The aerosol extinction coefficient is retrieved directly from the lidar return signal at the “off” wavelength and is used to estimate aerosol effects on O₃ and SO₂measurements. Null error, statistical error, and absorption cross-section error are also analyzed. The O₃ and SO₂ concentrations at height between 1000 m and 2000 m for a volcanic event on September 10, 2001 were about 20 ppb and 10–35 ppb, respectively, with an error less than 10 ppb. The measured SO₂ concentration was much higher than the normal SO₂ background value (∼1 ppb) in the troposphere. We also measured O₃ concentrations from 13 December 2000 to 06 January 2001 and investigated O₃ diurnal variation during a 24-hour period on November 24, 2000. A high O₃ concentration of about 250 ppb was observed in late December 2000. PACS 42.68.Wt; 42.68.Kh; 42.68.Jg     

Measurement of the transition strength of the 00o2 9.4 μm sequence band in CO2 using a tunable diode laser

We report the first accurate measurements of the transition strengths and linewidths of the 00^o2 9.4 μm sequence lines of CO₂. This sequence band is found to be very similar to the regular 00^o1 laser band, except for an experimentally determined factor of 1.89±0.12 increase in transition strength (if the CO₂ molecule is treated as a simple harmonic oscillator the theoretical increase in transition strength is 2.0). The laser absorption spectrometer used for these measurements can detect absorption coefficients in CO₂ of ≈10⁻⁷ m⁻¹, and we discuss the feasibility of using this sensitivity to monitor rare isotopic forms of CO₂. Work supported by the Department of National Health and Welfare, Environment Canada, Ontario Ministry of the Environment, and Atmospheric Environment Service, Environment Canada.     

Adsorption,Desorption, Dissoziation und Rekombination von SO2 an einer Palladium(111)-Oberfläche

Adsorption, Desorption, Dissociation and Recombination of SO₂ on a Palladium (111) Surface The adsorption, desorption as well as decomposition- and recombination-reactions of SO₂ on Pd(1 1 1) were studied for temperatures T = 160-1200 K using LEED, AES, thermal desorption-mass-spectrometry and molecular beam techniques. At 160 K SO₂ adsorption with an initial sticking coefficient s₀ = 1 is molecular and non-ordered; it is characterized by a precursor state and leads to a saturation coverage Θ ≈ 0,3. Heating up the adlayer SO₂ is the only desorption product, namely directly from (SO₂)_ad in the α-peak (T_max = 240 K) and as the product of recombination of (SO)_ad and O_ad in the β-peak (T_max = 330-370 K). A great part of the oxygen originating from SO₂-dissociation is incorporated into the subsurface region, resulting in an atomic S-adlayer with Θ_S = 1/7 which exhibits a (\documentclass{article}\pagestyle{empty}\begin{document}$ \sqrt 7 {\rm x}\sqrt 7 $\end{document}) R ± 19,1°-superstructure. This structure is also observed, if a 320 K-SO₂-exposure induced (2 × 2)-SO saturation layer with Θ_SO = 0,5 is heated up or if SO, is exposed at T > 500 K, where it corresponds to Θ_S, values of 3/7 and 2/7, respectively. Furthermore the poisoning effect of adsorbed sulfur on the dissociative O₂,-adsorption and the oxidation of sulfur by heating up an O? S-coadsorption layer were studied. As a result the following kinetic parameters (activation energies and frequency factors) were determined: .     

Infrared absorption of silane,ammonia, acetylene and diborane in the range of the CO2 laser emission lines: Measurements and modelling

Absorption spectra of the gases SiH₄, NH₃, C₂H₂ and of SiH₄/Ar and SiH₄/B₂H₆ mixtures have been measured in the spectral range of the CO₂ laser from 9.2 to 10.8 µm. In agreement with literature, silane shows the highest absorption (absorption coefficient = 3.3 × 10^–2 Pa^–1 m^–1). The deviation of the measured absorption behaviour of silane from literature, as far as the pressure dependence is concerned, can be explained by the enhanced spectral energy density in our experiment. This is confirmed by a rate-equation model involving the basic mechanisms of V-V and V-T energy transfer between vibrationally excited silane molecules. In contrast to silane, the absorption coefficient of NH₃ at the 10P(20) laser line is 4.5 × 10^–4 Pa^–1 m^–1 atp = 20 kPa and has its maximum of 4.5 × 10^–3 Pa^–1 m^–1 at the 10R(6) laser line. For C₂H₂ and B₂H₆, is even less ( 2.1 Ò 10^–5 Pa^–1 m^–1 for C₂H₂).     

A laser optical method for the determination of tropospheric OH concentrations

A long-path absorption procedure for the determination of tropospheric OH concentrations is described in detail. Initial measurements using this method were carried out in Frankfurt a. M. By including in the evaluation the visible radiation of a frequencydoubled dye laser used in the measurements, it was possible to mathematically reduce the signal fluctuations caused by the scattering and density fluctuations of tropospheric air. The resulting detection limit was 3×10⁶ OH per cm³. SO₂ concentrations which had to be simultaneously determined in order to eliminate an interference effect, could be detected in the range of 1–40 ppb on the absorption path.     

Laser stark spectroscopy ofSO2 with the HCN laser

The Far Infrared (FIR) laser Stark spectrum ofSO ₂ was investigated using the 337 m line of the HCN laser. Two distinct families, one originating at low field and the other at high field, were observed. The high field transition is identified as theJ _K–1,K+1=22_5,1721_4,18, v₂=1 transition. A significant fourth-order Stark shift was observed for this transition in the presence of a large second-order Stark shift. The zero-field frequency of the assigned transition was obtained by accounting for the fourth-order contribution.Present Adress: Department of Chemistry, University of Rochester, Rochester, NY 14627.     

Preparation of RE<Subscript>2</Subscript>O<Subscript>2</Subscript>SO<Subscript>4</Subscript> (RE=La,Pr-Lu) microspheres from rare-earth-based infinite coordination polymers

Rare-earth-based infinite coordination polymer (RE-ICP) spheres with diameters ranging from 50 nm to 2 μm have been prepared using meso-2,3-dimercaptosuccinic acid (DMSA) as ligand under hydrothermal conditions. RE₂O₂SO₄ microspheres with similar morphology were obtained by calcining the corresponding RE-ICP spheres. However, as for Ce-ICP and Sc-ICP, CeO₂ and Sc₂O₃ were obtained. The products were characterized using X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, infrared spectroscopy, laser Raman spectrometry, and energy-dispersive X-ray spectrum. Elemental analysis and inductive coupled plasma atomic emission spectrometer were adopted to study the composition of the Eu-ICP. To explore their potential applications, several samples of the products were selected and their properties were investigated. The Eu-ICP and Eu₂O₂SO₄ microspheres give strong red emissions when excited with a 394-nm ultraviolet light. Furthermore, the Eu-ICP displays a high selectivity for Fe(III). The obtained CeO₂ has a strong absorption in the UV region and the Gd₂O₂SO₄ microspheres show paramagnetic behavior.

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Graphical abstract A series of RE₂O₂SO₄ microspheres were prepared using a coordination polymer precursor method.

     

Gain and excited singlet and triplet state absorption spectra of some 9-acetoxy-10(halogenoacetoxy)phenylanthracenes

An apparatus for, optical gain spectra measurements is described, which has been used to determine the gain spectra of several halogen substituted derivatives of 9-acetoxy-10(2-acetoxy)phenylanthracenes. Using the determinedS ₁- andT ₁-excited state absorption spectra and other spectroscopic data the gain spectrum have been computed. The changes of the determined laser parameters and spectroscopic data of the halogen substituted derivatives are discussed with reference to the intramolecular heavy atom effect.Work partially supported within the project CPBP01.06 and from the Foreign Commission at the University of Bremen     

Stimulated emission and laser action of Pr3+-doped YA1O3

Groundstate absorption, fluorescence, excited-state absorption, and stimulated emission of Pr:YA1O₃ were measured in dependence on the polarization. The results reflect the anisotropy of the host lattice. Especially the polarized spectra of the stimulated emission fit very well with the laser data of this material. Seven cw laser transitions in the visible spectral range obtained so far in Pr:YA1O₃ with argon-ion laser pumping were identified in the spectra of the stimulated emission. In addition, two infrared cw laser transitions were realized. The best results were achieved for the³ P ₀³ F ₄ laser transition at 746.9 nm with a maximum slope efficiency of 24.6%, a maximum output power of 49.6 mW, and a laser threshold of 25 mW.     

The effect of mid-infrared and far-infrared emission,generated at NH3 excitation by intense radiation of a TEA CO2 laser,on ammonia absorption

The effect of Mid-InfraRed (MIR) ( 12 m) and Far-InfraRed (FIR) ( 100 m) emission from excited ammonia on the absorption of intense radiation of a TEA CO₂ laser has been studied experimentally under collisional and collisionless excitation conditions with ammonia pressures from 0.5 to 0.03 Torr. The energy of MIR and FIR emission was studied as a function of NH₃ pressure and laser energy fluence. Particular emphasis was given to the kinetics of MIR and FIR emission generation at different NH₃ pressures and to the measurement of the time delay of re-emitted pulses relative to the exciting CO₂ laser pulse. It has been found that the re-emission in the MIR range is highly collisional in nature. The intensity of MIR emission drops sharply (asp ³) with decreasing NH₃ pressure and its delay time relative to the exciting laser pulse increases. At the same time, re-emission in the FIR range (in the case of resonant excitation of NH3 at the 9R (30) line of CO₂ laser) is observed during an exciting pulse up top < 0.03 Torr. When binding the rotational sub-levels of a molecule with transitions, FIR emission acts as rotational relaxation and thus leads to an increase in NH₃ IR absorption even at collisionless excitation.     

A tunable light source in the 370 nm range based on an optically stabilized,frequency-doubled semiconductor laser

A tunable harmonic output power of 18 W at a wavelength of =370 nm is obtained by resonance-enhanced frequency doubling of an optically-stabilized semiconductor laser. A commercially available AlGaAs laser diode which emits a maximum power of 10 mW at =740 nm is operated in an extended-cavity configuration. Dispersion prisms are used in the extended cavity to obtain longitudinal-mode selection with low loss of optical power. The output is focussed into an optically isolated high-finesse ring resonator which contains a LiIO₃ crystal for second-harmonic generation. One potential application of this laser source is the optical excitation and laser cooling of ytterbium in an ion trap. In a related demonstration experiment, the frequency-doubled diode laser is applied to excite the =369.5 nm ² S _1/2-² P _1/2 transition of ytterbium ions in a hollow-cathode discharge.     

3W average power 4.3 μm CO2 laser

A 3 W average power CO₂ laser oscillating in the range of 4.3m (10°1 to 10°O transition) is described. At the same time, the laser can emit 100 W in the sequence band 00°2 to 10°1 (10.6m). It is based on a commercial system with continuous-wave discharge of 12 m length and a slow gas flow. It operates in the Q-switched mode at pulse repetition rates up to 15 kHz. The pulse peak power is 1 kW and the pulse duration is 200 ns. The deviation from the theoretical efficiency limit has been decreased by a factor 2.5 in our device, due to saturation of the pumping (sequence band) radiation. We predict an improvement by another factor of 5 (possible average power of 10 to 20 W), if one avoids the absorption in the discharge-free zones.     

The characteristics of multiple-photon absorption of SF6 molecules cooled in free jet expansion from a pulsed supersonic nozzle

The multiple-photon absorption of pulsed TEA CO₂ laser radiation by SF₆ molecules cooled toT _R40K andT _v160K in the free jet expansion from a pulsed supersonic nozzle has been investigated at energy fluences of 0.1 to 3.0 J·cm^–2.For practically all laser lines which coincide with the linear absorption spectrum of thev ₃ vibrational mode of SF₆ [P(12)...P(28), 10,6 m], the dependence of the absorbed energyE _ab on the exciting energy fluence was found to be steeper than linearE _abⁿ, wheren=(1.1 to 1.8). Considerable increases of the absorption cross sections with increasing energy fluence were observed.The fraction of the molecules interacting with the laser radiation is estimated.     

Detailed vibrational population distributions in a CO2 laser discharge as measured with a tunable diode laser

A tunable diode laser (TDL) operating in the 2150–2350 cm^–1 wavenumber region is used to probe a conventional cw CO₂ laser discharge. Absorption lines in more than 25 different vibrational bands are observed, enabling us to determine absolute vibrational populations inall levels of concern to the dynamics of the 10 m CO₂ laser. Levels in thev ₃ mode of CO₂ as high as 00°9 are monitored, and it is found that anharmonic effects play a significant role in the populations of such levels. Thev ₁ andv ₂ mode populations are also investigated in detail, and it is found that these modes are strongly coupled and maintain a common vibrational temperature under all discharge conditions. The use of a TDL is shown to be a powerful technique for investigating the dynamics of infrared molecular lasers.This work was supported in part by the National Science and Engineering Research Council, Canada     

Berenstein-Zelevinsky triangles,elementary couplings,and fusion rules

We present a general scheme for describing (N) _k fusion rules in terms of elementary couplings, using Berenstein-Zelevinsky triangles. A fusion coupling is characterized by its corresponding tensor product coupling (i.e. its Berenstein-Zelevinsky triangle) and the threshold level at which it first appears. We show that a closed expression for this threshold level is encoded in the Berenstein-Zelevinsky triangle and an explicit method to calculate it is presented. In this way, a complete solution of (4) _k fusion rules is obtained.Work supported by NSERC (Canada).Work supported by NSERC (Canada) and FCAR (Québec).     

Infrared laser stark shift spectroscopy in ammonia

The Stark effect in ammonia has been theoretically and experimentally analyzed using lead salt tunable diode laser absorption spectroscopy and CO₂ laser absorption spectroscopy of several absorption lines around 1050 cm^–1 applied to an all-optical sensor for measuring of electric field strength. Measurements of the Stark splitting effect of theaR(5,K) ammonia lines forK=1–5 as well as for the sR(3,K) lines forK=0–3 have been made at Doppler broadening pressures and for several different electric field strengths. Theoretical electric field dependent energy levels have been evaluated by diagonalization of a 6×6 energy matrix constructed using both electric field independent and dependent terms. From the theoretical analysis the resolution can be predicted and optimized both in the Doppler broadened and in the pressure broadened regimes. The predicted resolution is 0.5% at an electric field strength of 20 kV/cm. The theoretical calculations and the experimental data recorded with the tunable diode laser system were compared with independent measurements made with a CO₂ laser system. The agreement between experimentally recorded and theoretically calculated spectra is good which indicates that the theoretical model is satisfactory for our purposes. The contribution from the normally forbidden ssR(5, 3) ammonia line to the absorption at theP(12) CO₂ laser line in the 9 m band is briefly discussed.