Tunable KrF laser-induced fluorescence of C2 in a sooting flame

2 in a flame, excited by a tunable KrF laser near 248 nm. The first comprises several P and R lines of the (1,0) band of the e ³Π_g-a ³Π_u Fox–Herzberg system, with fluorescence bands extending past 350 nm. The second is the band head region of the (7,1) band of the D ¹Σ_u ⁺←B^′ 1Σ_g ⁺ system, with fluorescence at 232 nm from D to the X ¹Σ_g ⁺ ground state. Neither band has been previously observed in any environment. The flame in these experiments is highly sooting, and the C₂ seen here is likely produced by laser vaporization of the soot with subsequent laser photolysis of a C₂ precursor. In a rich flame, this fluorescence could cause interferences in other studies such as KrF laser Raman scattering. Moreover, signal level calculations suggest native C₂ near 10 ppm could be readily observed using the Fox–Herzberg excitation. Raman measurements of major species (X≥0.01) in the same flame, using the KrF laser, are in good agreement with a model prediction. Received: 2 April 1998/Revised version: 8 June 1998     

Quantitative NO-LIF imaging in high-pressure flames

Planar laser-induced fluorescence (PLIF) images of NO concentration are reported in premixed laminar flames from 1–60 bar exciting the A-X(0,0) band. The influence of O₂ interference and gas composition, the variation with local temperature, and the effect of laser and signal attenuation by UV light absorption are investigated. Despite choosing a NO excitation and detection scheme with minimum O₂-LIF contribution, this interference produces errors of up to 25% in a slightly lean 60 bar flame. The overall dependence of the inferred NO number density with temperature in the relevant (1200–2500 K) range is low (<±15%) because different effects cancel. The attenuation of laser and signal light by combustion products CO₂ and H₂O is frequently neglected, yet such absorption yields errors of up to 40% in our experiment despite the small scale (8 mm flame diameter). Understanding the dynamic range for each of these corrections provides guidance to minimize errors in single shot imaging experiments at high pressure. Received: 13 May 2002 / Published online: 8 August 2002     

Photochemical effects of KrF excimer excitation in laser-induced fluorescence measurements of OH in combustion environments

This paper presents experimental evidence that using the KrF excimer laser for quantitative laser-induced fluorescence (LIF) studies of the OH A-X (3,0) system is highly problematic if the effects of both photobleaching and photochemistry are not included for laser spectral irradiances greater than 20 MW/cm² cm^-1. Pump-probe and time-resolved measurements of the OH LIF signal in an atmospheric pressure, premixed CH₄-air flame at low- and high-laser-spectral-irradiance conditions show that a significant amount of OH is produced from photofragments resulting from the simultaneous 2-photon predissociation of H₂O molecules in the C-X system. A 5+2-level rate-equation model that includes the effects of both photobleaching and photochemical OH production is shown to satisfactorily predict the data using a single adjustable parameter given by the effective, spectrally integrated 2-photon cross-section of H₂O near 248 nm. The time-integrated OH LIF signal was found to depend on both the laser spectral irradiance and the local concentration of H₂O. Additionally, use of the KrF excimer laser for 2-line rotational thermometry can produce temperature errors as great as +550 K at high laser-pulse energies. Received: 21 August 2000 / Revised version: 30 October 2000 / Published online: 21 February 2001     

Experimental study of signal trapping of OH laser induced fluorescence and chemiluminescence in flames

The absorption of OH^∗ chemiluminescence and laser-induced fluorescence (LIF) in the exhaust gas of confined premixed laminar CH₄/air flames at atmospheric pressure was investigated. One flame was used as source and a second as absorber. OH LIF was excited in the ν″=0→ν′=1 band of the A–X electronic system around ≈283 nm and spectrally resolved detected in the (0,0) and (1,1) vibrational bands around 305–320 nm. For OH^∗ chemiluminescence, spectrally resolved detection was performed in the wavelength range 280–340 nm. For an absorption path of 54 mm and at T≈2000 K, signal trapping on the order of 10–40% was observed. Signal trapping was most pronounced in the (0,0) band, as expected from the thermal population distribution of OH in the electronic ground state. The spectral distribution of the signals and the wavelength dependence of the signal trapping are addressed in this paper. Implications from the results with respect to detection strategies and chemiluminescence-based equivalence ratio measurements are discussed.     

REMPI as a tool for studies of OH radicals in catalytic reactions

2 +? O₂→H₂O on polycrystalline Pt foils has been studied by detection of desorbing OH radicals using the Resonance Enhanced Multiphoton Ionization, REMPI, technique. The measurements were performed at catalyst temperatures of 1000–1400 K and a total pressure below 10^-4 mbar. The studies of OH desorption by REMPI were achieved using a two-photon excitation D²Σ^-–X²Π (1–0), followed by one-photon ionization. The ions were detected in a time-of-flight mass spectrometer, TOF-MS, in order to avoid interference from non-resonantly ionized molecules. By applying TOF-MS, a simultaneous non-resonant ionization and detection of H₂, O₂ and H₂O was achieved. Recorded REMPI spectra were compared with spectra simulated using known molecular constants. The kinetics of the reaction derived from the measurements were compared with what was obtained in earlier LIF detection of OH, performed at higher total reactant pressure using the A–X transition. REMPI TOF-MS is shown to be a complement to LIF for reaction studies below 5×10^-4 mbar total pressure, where LIF is too insensitive for quantification. The reaction kinetics was found to be in agreement with a theoretic model and previous LIF studies. Received: 8 March 1996/Revised version: 4 October 1996     

OH number densities and plasma jet behavior in atmospheric microwave plasma jets operating with different plasma gases (Ar,Ar/N<Subscript>2</Subscript>, and Ar/O<Subscript>2</Subscript>)

OH radical number density in multiple atmospheric pressure microwave plasma jets is measured using UV cavity ringdown spectroscopy of the OH (A–X) (0–0) band at 308 nm. The plasma cavity was excited by a 2.45 GHz microwave plasma source and plasma jets of 2–12 mm long were generated by using three different plasma gases, argon (Ar), Ar/N₂, and Ar/O₂. Comparative characterization of the plasma jets in terms of plasma shape, stability, gas temperature, emission intensities of OH, NO, and N₂, and absolute number density of the OH radical was carried out under different plasma gas flow rates and powers at various locations along the plasma jet axis. With three different operating gases, the presence of OH radicals in all of the plasma jets extended to the far downstream. As compared to the argon plasma jets, the plasma jets formed with Ar/N₂ and Ar/O₂ are more diffuse and less stable. Plasma gas temperatures along the jet axis were measured to be in the range of 470–800 K for all of the jets formed in the different gas mixtures. In each plasma jet, OH number density decreases along the jet axis from the highest OH density in the vicinity of the jet tip to the lowest in the far downstream. OH density ranges from 1.3 × 10¹² to 1.1 × 10¹⁶, 4.1 × 10¹³ to 3.9 × 10¹⁵, and 7.0 × 10¹² to 4.6 × 10¹⁶ molecule/cm³ in the Ar, Ar/N₂, and Ar/O₂ plasma jets, respectively. The OH density dependence on plasma power and gas flow rate in the three plasma jets is also investigated.     

Short-wavelength far-infrared laser cavity yielding new laser emissions in CD3OH

A significantly improved far-infrared laser has been used to generate optically pumped laser emissions from 26 to 150 μm for CD₃OH. Using an X–V-pumping geometry, several new laser emissions have been found for CD₃OH. In addition, an increase in power, by factors from 10 to 1000, for many of the previously known shorter-wavelength laser lines, below 100 μm, has been observed. Frequency measurements for several lines have also been performed and have been reported to a fractional uncertainty up to ±2×10^-7, permitting the spectroscopic assignment of the laser transition. One of the frequency-measured lines, 44.256 μm observed using the 10R34 pump, has confirmed the assignment of the previously reported FIR emission (n,K;J)=(1,7;20)?(0,8;20)A in the ground vibrational state. Received: 26 October 2000 / Published online: 7 February 2001     

New short-wavelength laser emissions from partially deuterated methanol isotopes

The partially deuterated isotopes of methanol, CH₂DOH and CHD₂OH, have been reinvestigated as sources of far-infrared (FIR) laser emissions using an optically pumped molecular laser (OPML) system recently designed for wavelengths below 150 μm. With this system, 10 new FIR laser emissions from these isotopes ranging from 32.8 to 174.6 μm have been discovered. This includes the shortest known OPML emission from CHD₂OH, at 32.8 μm. These lines are reported with their operating pressure, polarizations relative to the CO₂ pump laser and wavelengths, measured to ±0.5 μm. In addition, polarizations for three previously observed FIR laser lines from CHD₂OH were measured for the first time. This paper is dedicated to the memory of Dr. K.M. Evenson, a pioneer in the field for his role in the development of optically pumped molecular lasers and their use in laser frequency measurements and the laser magnetic resonance technique. His scientific expertise, guidance, mentoring and friendship will be greatly missed. Received: 27 March 2002 / Published online: 8 May 2002     

Investigations of electronic minority charge carrier conductivity in La0.9Sr0.1Ga0.8Mg0.2O2.85

The perovskite structured material LaGaO₃ doped with 10 mol-% strontium and 20 mol-% magnesium was prepared by two different wet-chemical synthesis routes. The total conductivity was measured in air and under an oxygen partial pressure of 10⁻²⁰ bar. There was a decrease by 10 % in 4 days when the atmosphere was changed from air to 10⁻²⁰ bar. This process is reversible. Hebb-Wagner measurements resulted in values for the electronic minority charge carrier conductivities in pure oxygen of log σ_h [S/cm]=−4.02 and log σ_e [S/cm]=−15.5 for the holes and electrons, respectively, at 600 °C. In the partial pressure range 10⁻³ bar≤p(O₂)≤1 bar, a slope of +1/4 was observed for d(log (σ_h)) / d(log (p(O₂)) at T=600, 650 and 700 °C. That is in agreement with the assumption of a large number of oxygen vacancies. The diffusion coefficient of the holes was evaluated from the relaxation curves to be 1.1*10⁻⁷ cm²/s at 600 °C. Degradation effects were observed under highly reducing conditions which are attributed to the formation of gallium-platinum alloys and the loss of gallium oxide if O₂ is available in the gas phase. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Wavelength-agile fiber laser using group-velocity dispersion of pulsed super-continua and application to broadband absorption spectroscopy

A swept-wavelength source is created by connecting four elements in series: a femtosecond fiber laser at 1.56 μm, a non-linear fiber, a dispersive fiber and a tunable spectral bandpass filter. The 1.56-μm pulses are converted to super-continuum (1.1–2.2 μm) pulses by the non-linear fiber, and these broadband pulses are stretched and arranged into wavelength scans by the dispersive fiber. The tunable bandpass filter is used to select a portion of the super-continuum as a scan-wavelength output. A variety of scan characteristics are possible using this approach. As an example, an output with an effective linewidth of approximately 1 cm^-1 is scanned from 1350–1550 nm every 20 ns. Compared to previous scanning benchmarks of approximately 1 nm/μs, such broad, rapid scans offer new capabilities: a gas sensing application is demonstrated by monitoring absorption bands of H₂O, CO₂, C₂H₂ and C₂H₆O at a pressure of 10 bar. Received: 5 August 2002 / Revised version: 23 September 2002 / Published online: 22 November 2002 RID="*" ID="*"Corresponding author. Fax: +1-608/265-2316, E-mail: ssanders@engr.wisc.edu     

Quasi-simultaneous detection of CH2O and CH by cavity ring-down absorption and laser-induced fluorescence in a methane/air low-pressure flame

The combination of two-dimensional, planar laser-induced fluorescence (PLIF) and cavity ring-down (CRD) absorption spectroscopy is applied to map quantitatively the spatial distributions of CH₂O and CH in a methane/air flame at 25 Torr. Both species are detected in the same spectral region using the overlapping CH₂O A ¹ A ₂ -X ¹ A ₁ 4₁ ⁰ and CH B-X(1,0 )bands. The combination of diagnostic techniques exploits the spatial resolution of LIF and the quantitative CRD absorption measure of column density. The spatially resolved PLIF provides the distribution of absorbers and line-of-sight CRD absorption the absolute number density needed for quantitative concentration images. The peak CH₂O concentration is (3.5±1.4 )×10¹⁴ cm^-3, or 1450±550 ppm at 1000 K. The lack of precise absorption cross-section data produces these large error limits. Although a flame model predicts lower amounts, these large uncertainties limit this measurement’susefulness as a test of the flame chemistry. Received: 24 April 2001 / Revised version: 10 July 2001 / Published online: 10 October 2001     

Analysis of degenerate four-wave mixing spectra of NO in a CH4/N2/O2 flame

4 /N₂/O₂ flame to spectral simulations based on a two-level theory for stationary, saturable absorbers by Abrams et al. Temperatures determined from least-squares fits of simulations to experimental spectra in the A²Σ⁺?X²Π⁺(0,0) band are compared to temperatures obtained from OH absorption spectroscopy and a radiation-corrected thermocouple. We find that DFWM rotational temperatures derived from Q-branch spectra agree with thermocouple and are independent of pump laser intensity for low to moderate saturation (I≈I_sat). However, the temperatures are systematically low and depend on pump intensity if the analysis neglects saturation effects. We demonstrate a method for obtaining an effective pump saturation intensity for use with the two-level model. This approach for analyzing saturated DFWM line intensities differs from previous work in that the use of the theory of Abrams et al. rather than a transition-dipole-moment power law allows treatment of a much wider range of saturation. Based on the observed signal-to-noise ratio an NO detection sensitivity of 25 ppm is projected, limited by a DFWM background interference specific to hydrocarbon flames. Received: 15 September 1998 / Revised version: 18 November 1998 / Published online: 24 February 1999     

Reference electrode formation in potentiometric CO2 sensors with alkali ion conducting alumosilicate glasses as solid electrolytes

Potentiometric CO₂ gas sensors with Li conducting glasses/glass ceramics of the system Li₂O-Al₂O₃-SiO₂ (different nominal composition) as solid electrolytes have been investigated. Li₂CO₃ was used as CO₂ and O₂ sensitive auxiliary electrode. During the sensor test measurements, the CO₂ partial pressure was varied between 1×10⁻³ and 1×10⁻¹ bar at a constant O₂ partial pressure of 2.1×10⁻¹ bar whereas N₂ was used as carrier gas. Comparative measurements were accomplished with sensors comprising Na and K ion conducting glasses. A metastable reference electrode was formed at the contact zone between the Au metal electrode and the former Li glasses of definite nominal composition by crystallization processes taking place, which lead to stable, reproducible CO₂ dependent EMF signals for more than 90d. The thermodynamically expected EMF difference and the observed EMF difference agree quite well between 500 and 600 °C. At 600 °C, the drift of sensors with glasses as solid electrolytes and direct Au glass/glass ceramics contact as reference electrode amounts typically 0.32 mV/d (p(CO₂)=1×10⁻³ bar, p(O₂)=2.1×10⁻¹ bar at the measuring electrode), if a metastable multiphase equilibrium is formed. At identical partial pressures of CO₂ and O₂, the signal reproducibility of these sensors with different solid electrolyte glasses of the same nominal composition lies within 30 mV at 600 °C. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Single-shot laser-induced fluorescence imaging of formaldehyde with XeF excimer excitation

Single-shot formaldehyde laser-induced fluorescence (LIF) imaging measurements in a technical scale turbulent flame have been obtained using XeF excimer laser excitation in the ?¹A₂-˜X¹A₁ transition at 353.2 nm. Measurements have been carried out in a 150 kW natural gas swirl burner where formaldehyde distribution fields have the potential, in combination with OH concentration fields, to visualize the heat release distribution and therefore give an optimal visualization of flame-front positions. The extended areas where formaldehyde was detected in the swirl flame indicates the presence of low temperature chemistry in preheated gas pockets before ignition. Received: 31 January 2000 / Revised version: 2 March 2000 / Published online: 5 April 2000     

Measurement of vibrational energy transfer of OH (A2Σ+,v′=1→0) in low-pressure flames

2 Σ⁺) was measured in a low-pressure H₂/O₂ flame for three rotational levels of OH (v^′=1). Rate coefficients for collisions with H₂O and N₂ were determined. At 1600 K, k_VET (N₂) is (in 10^-11 cm³s^-1) 10.1±2, 6.1±1.8, and 3.8±1.3 for N^′=0, 5, and 13, respectively. The k_VET (H₂O) is <1.1±1.8. The k_Q (N₂) is <2.4±8 for both vibrational levels. The k_Q (H₂O) in v^′=1 is 59.1±6.5, 54.7±6.4, and 54.9±6.6 for N^′=0, 5, and 13, respectively, and, determined indirectly, 74.6±10.4, 70.6±10.3, and 63.4±7.3 for N^′=0, 5, and 13 in v^′=0. A multi-level model of OH population dynamics, which is being developed for the quantitative simulation of experimental LIF spectra, was extended to include VET. It was attempted to simulate state-to-state-specific VET coefficients for N₂ collisions. From these simulations it appears that angular momentum conservation does not determine the N dependence of the vibrational relaxation step. Received: 9 September 1996/Revised version: 6 January 1997     

Mid-infrared polarization spectroscopy of carbon dioxide

The use of mid-infrared polarization spectroscopy (PS) for the detection of CO₂ has been demonstrated. The P(13) and P(14) resonances of the (0 0⁰ 0)→(1 0⁰ 1) transition of CO₂ were probed using a single-mode optical parametric generator system to produce a high-intensity laser beam at approximately 2.7 μm. The experiments were performed in an atmospheric pressure CO₂ jet and also in a sub-atmospheric pressure gas cell. The experimental results were compared with the results of the time-dependent density-matrix equations using direct numerical integration. The Zeeman-state structure of the upper and lower energy levels was included in the multi-state formulation of the density-matrix equations. Fifty-eight Zeeman states and two bath levels were included in the numerical analysis of the P(14) transition. The measured and calculated PS line shapes were in good agreement, and the absolute experimental signal level agreed with the theoretical calculation to within a factor of five. Received: 20 March 2002 / Revised version: 16 August 2002 / Published online: 11 December 2002 RID="*" ID="*"Present address: Innovative Scientific Solutions Inc., 2766 Indian Ripple Road, Dayton, OH 45 440, USA RID="**" ID="**"Corresponding author. Fax: +1-765/494-0539, E-mail: Lucht@purdue.edu RID="***" ID="***"Present address: School of Mechanical Engineering, Purdue University, W. Lafayette, IN 47807-2040 USA     

High spin states and evidence for octupole correlations in 117Xe

High-spin states of ¹¹⁷Xe were investigated by means of in-beam γ-ray spectroscopic techniques via the reaction of ²⁸Si bombarding a ⁹²Mo target at beam energies of 100-120 MeV. A positive-parity rotational band decaying into the yrast negative-parity band by a series of enhanced E1 transitions was observed for the first time, implying the existence of octupole correlations in ¹¹⁷Xe. The B(E1) values increase with spin. The νd_5/2 band was firmly established up to 27/2⁺ and the B(M1)/B(E2) ratios were extracted from the relative intensities of γ-rays in this band. The previously known νh_11/2 and νg_7/2 [413]5/2⁺α=−1/2 bands were confirmed and extended up to high spins and two bandcrossings are observed in the latter at ħω=0.33 and 0.44 MeV, respectively. The bandcrossings and configurations of these bands are discussed by TRS and CSM calculations. In a γ–γ–t measurement, the 11/2⁻ and 7/2⁻ levels were identified as two isomers with half-lives of 59.4±20 ns and 16.5±8.0 ns, respectively. Received: 17 June 1997 / Revised version: 29 September 1997     

High-spin states of rotational bands built upon νi13/2 in 166Lu

High-Spin states of odd-odd ¹⁶⁶Lu were populated using the ¹³⁹La(³⁰Si,3nγ)¹⁶⁶Lu at a beam energy of 120 MeV. Twelve new γ-rays were placed on top of the previously known two rotational bands built upon πg _7/2⊗νi _13/2 and πh _11/2⊗νi _13/2. Extending high-spin states up to 21⁺ and 25⁻ for each band, we have observed the onset of band crossing near ħω _c ≈ 0.35 MeV. The band crossing frequency of the yrast πh _11/2⊗νi _13/2 band is consistent with the neutron BC band crossing observed in lighter odd-odd Lu isotopes.     

First observation of the ν9/2[404] orbital in the A ∼ 100 mass region

A new band, populated by the spontaneous fission of ²⁴⁸Cm and studied by means of prompt γ-ray spectroscopy using the EUROGAM2 array, was observed in ⁹⁹Zr. The 1038.8 keV band head with a half-life T _1/2 = 54(10) ns is interpreted as a K-isomer, corresponding to the 9/2[404] neutron-hole excitation. It is the first observation of this orbital in the mass A ∼ 100 region. The quadrupole moment, Q ₀ = 3.9(3) eb deduced for the new band indicates a large deformation of β = 0.41, which is produced by a specific shape-coexistence mechanism, known in other regions and now found in the A ∼ 100 nuclei. Received: 11 September 2002 / Accepted: 31 October 2002 / Published online: 17 January 2003 RID="a" ID="a"e-mail: urban@fuw.edu.pl Communicated by D. Schwalm     

Crystalline structure and optical spectroscopy of Er3+-doped KGd(WO4)2 single crystals

4 )₂ single crystals doped with Er³⁺ have been grown by the flux top-seeded-solution growth method. The crystallographic structure of the lattice has been refined, being the lattice constants a=10.652(4), b=10.374(6), c=7.582(2) Å, β=130.80(2)°. The refractive index dispersion of the host has been measured in the 350–1500 nm range. The optical absorption and photoluminescence properties of Er³⁺ have been characterised in the 5–300 K temperature range. At 5 K, the absorption and emission bands show the (2J+1)/2 multiplet splittings expected for the C₂ symmetry site of Er in the Gd site. The energy positions and halfwidths of the 72 sublevels observed have been tabulated as well as the cross sections of the different multiplets. Six emission band sets have been observed under excitation of the ⁴F_7/2 multiplet. The Judd–Ofelt (JO) parameters of Er³⁺ in KGW have been calculated: Ω₂=8.90×10^-20 cm², Ω₄=0.96×10^-20 cm², Ω₆=0.82×10^-20 cm². Lifetimes of the ⁴S_3/2, ⁴F_9/2, and ⁴I_11/2 multiplets have been measured in the 5–300 K range of temperature and compared with those calculated from the JO theory. A reduction of the ⁴S_3/2 and ⁴I_11/2 measured lifetimes with increasing erbium concentration has been observed, moreover the presence of multiphonon non-radiative processes is inferred from the temperature dependence of the lifetimes. Received: 15 December 1997/Revised version: 10 July 1998