A tunable laser at λ=3.39 μm with line width of 7 Hz used in investigating a hyperfine structure of theF 2 (2) line of methane

A laser spectrometer is described which was used in exploring resonance shapes of about 1000 Hz width in methane in the region of low absorption of about 10⁻⁶ cm⁻¹. We report on first measurements of relative intensities of hyperfine components of theF ₂ ⁽²⁾ line in methane, on direct observations of line splitting due to a recoil effect and of a non-linear dependence of collisional broadening of resonances in the transit region, and on observation of an anomalous Zeeman effect in hyperfine components in a longitudinal magnetic field. The results of this work were summarized by one of the authors (V.C.) at the 2nd Symposium on Frequency Standards and Metrology (Boulder, Colo., USA, July 1976) and at lectures in the School Enrico Fermi (Varenna, Italy, July 1976).     

Diode-laser spectroscopy: Temperature dependence of R (0) line in the ν4 band of CH4 perturbed by N2 and O2

In this paper, we present a line profile study of the R (0) line in the ν₄ band of methane diluted in nitrogen and oxygen, from room temperature to 153 K. The measurements were performed over a total pressure range from 14 to 128 mbar. The collisional broadening and narrowing (Dicke effect) coefficients are derived from a fit of the experimental spectra by using the soft and hard collision models, taking into account the Dicke effect. For higher pressures, we have fitted the data with a model taking into account simultaneously the Dicke narrowing and the speed dependence effect. Finally, we have deduced the parameter n of the temperature dependence (inverse power law) of the broadening coefficients for the CH₄-N₂ and CH₄-O₂ gas mixtures.     

Self and N2 collisional broadening of far-infrared methane lines measured at the SOLEIL synchrotron

Following our recent study devoted to measurements of intensities of pure rotation lines of methane, room temperature far infrared spectra of methane diluted in nitrogen at five total pressures between 100 and 800 hPa have been recorded at the AILES beamline of the SOLEIL synchrotron. One hundred and five N₂ broadening coefficients of methane pure rotation lines have been measured in the 83–261 cm^?1 spectral range using multi-spectrum non-linear least squares fitting of Voigt profiles. Pressure-induced line shifts were not needed to fit the spectra to the noise level and line mixing effects were neglected. One hundred and seventy-six self broadening coefficients have also been measured in the 59–288 cm^?1 spectral range using the pure methane spectra recorded in our previous work. The measured N₂ broadening coefficients were compared to semi-classical calculations.     

Self-, N2- and O2-broadening coefficients for the CO2 transitions near-IR measured by a diode laser photoacoustic spectrometer

Using a high-resolution tunable diode laser photoacoustic spectrometer, self-, N₂ and O₂ pressure broadening coefficients for the first 11 transitions of ¹²C¹⁶O₂ in the R branch of the (30012) ← (00001) overtone band at the 6348 cm⁻¹ have been revisited at room temperature (∼298 K). Air-broadening parameters have also been calculated from the N₂ and O₂ measurements. The dependence of the broadening on rotational quantum number m is discussed. The recorded lineshapes are fitted with standard Voigt line profiles in order to determine the collisional broadening coefficients of carbon dioxide transitions. The results are compared to our previous measurements and to the values reported in the HITRAN04 database and by other research group with a different spectroscopic technique.     

Some remarks on the ionic conductivity in NaY dehydrated zeolite

On the basis of experimental measurements of the electrical conductivity of the Nafaujasite zeolites (NaY), treated under vacuum up to 673 K for 24 hours, we clearly demonstrate that the behavior of the measured conductivity σ_ac of the dehydrated zeolite NaY, over an interval of high frequency change, may be described by a power-law function: σ_ac=A▹^s. The exponent s, in this case, should be considered as temperature and frequency dependent when the parameter A is a temperature dependent function. On the other hand, when considering the measured conductivity as a sum of two terms (σ_ac=σ₀+σ′(▹)) resulting from the contributions of the dc and the ac components respectively, we find that one of them obeys the Arrhenius law while the other can be expressed as A▹^s. Parameter s is practically frequency independent when the frequency of the applied electrical field is higher than a characteristic value ▹_c A comparison with the measurements performed on NaY dehydrated at 435 K is also included. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

N2-, H2-, and He-induced collisional broadening of the J = 24 ← 23 transition of HC3N located near 218.3 GHz at different temperatures

We report on experimental collisional relaxation of the J = 24 ← 23 line of HC₃¹⁴N, located near 218.3 GHz, induced by nitrogen, hydrogen, and helium. The measurements were carried out at selected temperatures in the 235-350 K range using a video-type spectrometer. The foreign gas broadening parameters and their temperature dependences were determined assuming Voigt lineshape profiles and the usual T⁻ⁿ temperature law. The experimental broadening parameters are compared with results derived using the ATC collisional formalism.     

The CH3D absorption spectrum in the 1.58 μm transparency window of methane: Empirical line lists at 81 K and 294 K and temperature dependence

In spite of its low isotopic abundance in methane (about 5×10⁻⁴), CH₃D contributes greatly to the very weak absorption in the 1.58 μm methane transparency window. This methane window deserves to be characterized in details because it is important for planetary applications in particular for Titan and the giant planets. In this work, we recorded the CH₃D spectrum by high sensitivity differential absorption spectroscopy (α_min≈5×10⁻⁸ cm⁻¹) both at room temperature and at 81 K. A list of more than 9000 lines was constructed from the 81 K spectrum for the 6099–6530 cm⁻¹ region. In order to get the temperature dependence of the line intensities, the low energy values have to be determined. The rovibrational assignments available in the literature provide low energy values for about 380 strong transitions of the region. This is insufficient to characterize the temperature dependence of the CH₃D absorption between 6200 and 6400 cm⁻¹. In this interval, a list of 5500 lines was constructed from the room temperature spectrum. The empirical energy values of the transitions were derived from the ratio of the intensities at 81 K and 294 K. The exact and empirical lower state energies included in the final line lists provided as Supplementary Material, allow for accounting for the temperature dependence of the CH₃D spectrum in the entire 6099–6530 cm⁻¹ region.Our measurements have been compared to the spectroscopic parameters and assignments available in the literature in particular those adopted in the HITRAN database. Improvements and corrections are proposed for the wavenumber calibration and for some lower state energies.     

Kinetic temperature and electron density measurement in?an?inductively coupled plasma torch using degenerate four-wave mixing

Laser wave mixing is presented as an effective technique for spatially resolved kinetic temperature measurements in an atmospheric-pressure radio-frequency inductively coupled plasma. Measurements are performed in a 1 kW, 27 MHz radio-frequency plasma using a continuous-wave, tunable 811.5 nm diode laser to excite the 4s³P₂→4p³D₃ argon transition. Kinetic temperature measurements are made at five radial steps from the center of the torch and at four different torch heights. The kinetic temperature is determined by measuring simultaneously the line shape of the sub-Doppler backward phase-conjugate degenerate four-wave mixing and the Doppler broadened forward-scattering degenerate four-wave mixing. The temperature measurements result in a range of 3,500 to 14,000±150 K. Electron densities measured range from 6.1 (±0.3)×10¹⁵ cm⁻³ to 10.1 (±0.3)×10¹⁵ cm⁻³. The experimental spectra are analyzed using a perturbative treatment of the backward phase-conjugate and forward-geometry wave-mixing theory. The Stark width is determined from the collisional broadening measured in the phase-conjugate geometry. Electron density measurements are made based on the Stark width. The kinetic temperature of the plasma was found to be more than halved by adding deionized water through the nebulizer.     

Temperature dependence of pressure broadening and shifts of acetylene at 1550 nm by He, Ne, and Ar

Pressure broadening and shift coefficients for the ν₁+ν₃ band of ¹²C₂H₂ have been measured for He, Ne, and Ar at a temperature of 195 K using high resolution diode laser spectroscopy. The pressure broadening and shifts follow patterns with rotational assignment that are similar to those at room temperature but are generally larger in magnitude. The change in magnitude is qualitatively described by assuming, for each transition, a constant cross section for pressure broadening or shifting. Better agreement may be obtained for pressure broadening coefficients by using empirically determined temperature exponents; better agreement still is obtained from close coupling calculations of the pressure broadening cross sections. PACS 33.70.Jg     

Measurement of the temperature dependence of line mixing and pressure broadening parameters between 296 and 90 K in the ν3 band of CH4 and their influence on atmospheric methane retrievals

We measured the temperature dependence of the nitrogen broadening, narrowing and line-mixing coefficients of four lines of the P9 manifold in the ν₃ band of ¹²CH₄ for atmospheric purposes. The data were collected using our tunable diode laser (TDL) spectrometer with active wavenumber control coupled to a newly developed cold Herriott cell with a path length of 5.37 m and a temperature uniformity of better than 0.01 K along the cell. We recorded and analyzed spectra recorded at sample temperatures between 90 K and room temperature. We have investigated the influence of our new results in the inversion model used to retrieve methane profiles from atmospheric spectra; our new results make it possible to retrieve significantly more precise methane profiles. The atmospheric spectra we utilized were obtained by several of us with a balloon-born Fourier Transform infrared experiment in a limb configuration. Differences up to 7% on the retrieved volume mixing ratio were found compared to an inversion model using only HITRAN04 spectroscopic parameters.     

Electric field gradients at the 111In site in the ferroelectric and paraelectric phases of LiTaO3

The temperature dependence of the electric-field gradient of ¹¹¹Cd in single crystalline LiTaO₃ was studied from room temperature to 1040 K in the ferroelectric and paraelectric phases. The data taken at room temperature show unambiguously the presence of two quadrupole interaction frequencies, ν_Q1=230 MHz and ν_Q2=242 MHz, with nonzero asymmetry parameters, while above the Curie temperature (T_C=878 K) the data are well described by a unique frequency. The electric field gradient shows a usual temperature dependence, increasing aproximately in a linear fashion until T_C and then decreasing faster. The initial increase is explained mostly by the lattice expansion, while above T_C it is necessary to consider Li and O displacements. This revised version was published online in August 2006 with corrections to the Cover Date.     

Continuous-wave cavity-ringdown detection of stimulated Raman gain spectra

Cavity ringdown (CRD) spectroscopy, with its high sensitivity, provides a novel way to perform continuous-wave (cw) stimulated Raman gain (SRG) spectroscopy, rather than by conventional optically detected coherent Raman techniques. Tunable cw laser light at ∼1544 nm is used to probe ringdown decay from a rapidly-swept, high-finesse optical cavity containing a gas-phase sample of interest and itself located inside the cavity of a cw single-longitudinal-mode Nd:YAG ring laser operating at ∼1064.4 nm. This approach is used to measure cw SRG spectra of the ν ₁ fundamental rovibrational Raman band of methane gas at ∼2916.5 cm⁻¹. The resulting SRG-CRD resonances have ringdown times longer than in the off-resonance case, in contrast to the usual shorter ringdown times arising from absorption and other loss processes. Previously reported noise-equivalent sensitivities have been substantially improved, by using a second ringdown cavity to facilitate subtraction of infrared-absorption background signals. Moreover, by employing a ringdown cavity in the form of a ring, the SRG-pump and CRD-detected Stokes beams can co-propagate uni-directionally, which significantly reduces Doppler broadening.     

Performance of a Herriott cell, designed for variable temperatures between 296 and 20 K

We designed, fabricated and tested a multipath Herriott cell (or off-axis spherical mirror interferometer) to achieve low temperature absorption measurements. The cell is fabricated entirely from copper, and the 15 cm radius of curvature copper mirrors have gold coated reflective surfaces. The cell was tested at temperatures between 296 and 20 K with a folded absorption path length of 5.37 m utilizing a lead salt tunable diode laser. Short term temperature stability (1 h) of the Herriott cell is better than 0.005 K under normal operating conditions with a temperature uniformity better than 0.01 K (not measurable). The cell was tested by performing collisional cooling experiments on ¹³C¹⁶O₂ in helium at temperatures between 70 and 20 K and by performing more traditional pressure broadening and shift measurements on molecular infrared absorption lines at temperatures between 300 and about 80 K on ¹³C¹⁶O₂ and methane.     

Trap characterization for Bi4Ti3O12 thin films by thermally stimulated currents

Thermally stimulated current (TSC) measurements performed in the 100 K–400 K temperature range on Bi₄Ti₃O₁₂ (BiT) thin films annealed at 550 °C and 700 °C had revealed two trapping levels having activation energies of 0.55 eV and 0.6 eV. The total trap concentration was estimated at 10¹⁵ cm⁻³ for the samples annealed at 550 °C and 3×10¹⁵ cm⁻³ for a 700 °C annealing and the trap capture cross-section was estimated about 10⁻¹⁸ cm². From the temperature dependence of the dark current in the temperature range 20 °C–120 °C the conduction mechanism activation energy was found to be about 0.956–0.978 eV. The electrical conductivity depends not only on the sample annealing temperature but also whether the measurement is performed in vacuum or air. The results on the dark conductivity are discussed considering the influence of oxygen atoms and oxygen vacancies. Received: 28 January 1998 / Accepted: 8 January 1999 / Published online: 5 May 1999     

Hyperfine Interactions in the Sr0.88Ba0.12HfO3 Compound

The temperature dependence of the hyperfine parameters in a powder sample of the Sr_0.88Ba_0.12HfO₃ compound has been investigated for the first time using perturbed angular correlation spectroscopy. The time spectra were measured as a function of the temperature from 293 to 1273 K. Activated ¹⁸¹Ta nuclei were used as hyperfine probes at the Hf sites. The analysis of the time spectra indicates the presence of two different surroundings for the Ta probes. The most populated site (f ₁≈75% at laboratory temperature) was fitted with the usual static quadrupole hyperfine interactions found in most perovskite-type compounds. The resulting quadrupole frequency is ω _Q ≈24 Mrad/s at this temperature. This frequency continuously decreases to nearly 9 Mrad/s at 1273 K. Its line width temperature dependence displays three regions and the changes observed probably correspond to phase transitions. The other site has a large and temperature independent quadrupole frequency ω _Q ≈120 Mrad/s that reversibly transforms into the first at high temperatures and probably originates from some defect in the structure. This revised version was published online in September 2006 with corrections to the Cover Date.     

Low and room temperature measurements and calculations of O2-broadening coefficients in the ν3 band of CS2

O₂-broadening coefficients have been measured for 16 lines in the P and R branches of the fundamental ν₃ band of ¹²C³²S₂ at room and low temperatures (298.0, 273.2, 248.2, 223.2, and 198.2 K), using a tunable diode laser spectrometer and a low temperature cell. These lines from P(62) and R(64) are located in the spectral range 1519-1547 cm⁻¹. The collisional half-widths are obtained by fitting each observed profile with the Voigt and Rautian lineshape models. The broadening coefficients have also been calculated at all experimental temperatures using a semiclassical calculation performed by considering in addition to the electrostatic quadrupole-quadrupole interaction, a simple anisotropic contribution. Finally, from all the results, the parameter n of the temperature dependence of the broadening coefficients has been determined both experimentally and theoretically.     

Line mixing effects in the ν2 + ν3 band of methane

This study provides the first direct experimental measurements of the off-diagonal relaxation matrix element coefficients for line mixing in air-broadened methane spectra for any vibrational band and the first off diagonal relaxation matrix elements associated with line mixing for pure methane in the ν₂ + ν₃ band of ¹²CH₄. The speed-dependent Voigt profile with line mixing is used with a multispectrum nonlinear least squares curve fitting technique to retrieve the various line parameters from 11 self-broadened and 10 air-broadened spectra simultaneously. The room temperature spectra analyzed in this work are recorded at 0.011 cm⁻¹ resolution with the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory, Kitt Peak, Arizona. The off-diagonal relaxation matrix element coefficients of ν₂ + ν₃ transitions between 4410 and 4629 cm⁻¹ are reported for eighteen pairs with upper state J values between 2 and 11. The observed line mixing coefficients for self broadening vary from 0.0019 to 0.0390 cm⁻¹ atm⁻¹ at 296 K. The measured line mixing coefficients for air broadening vary from 0.0005 to 0.0205 cm⁻¹ atm⁻¹ at 296 K.     

Cavity enhanced absorption spectroscopy measurements of?pressure-induced broadening and shift coefficients in?the?υ1+υ3 combination band of ammonia

Cavity enhanced absorption spectroscopy is performed using an external cavity diode laser operating around 1516 nm. We demonstrate a sensitivity of 6×10⁻⁸ cm⁻¹ Hz^−1/2 and utilise a simple method to measure pressure-induced broadening and shift coefficients. The broadening and shift coefficients for six gases (helium, neon, argon, xenon, oxygen and nitrogen) have been determined at room temperature for four transitions in the υ ₁+υ ₃ combination band of ammonia. Comparisons of the broadening coefficients with previous work in this region, where it exists, show good agreement. The broadening and shift coefficients of nitrogen and oxygen are also in good agreement with calculated values using the Robert and Bonamy theory. Both the broadening and shift coefficients show a clear trend through the rare gases, which can be explained in terms of the varying magnitude of the long range attractive forces operating between the colliding partners. We also demonstrate the application of the Parmenter–Seaver formalism to estimate the potential well depth of the ammonia dimer from the obtained broadening coefficients. The obtained well depth agrees well with theoretical calculations.     

Determination of the saturation parameter of electronic transition in a uranium-neon hollow-cathode discharge by optogalvanic spectroscopy

Summary The optogalvanic signal (OGS) induced in a uranium-neon hollow-cathode discharge was measured as a function of the laser power density for the 0→16900 cm⁻¹ (591.5 nm) uranium transition. Theoretical relations derived by solving a two-level system rate equations showed the OGS dependence on the laser photon flux, for a modulated c.w. light and for stimulated transitions starting from the ground state. A fitting of the theoretical relations to the experimental measurements allowed the determination of the σ₀ τ product, that is, the saturation parameter of the transition. The results showed good agreement between the σ₀ τ values obtained by the optogalvanic and the usual optical absorption processes.     

GOSAT-2009 methane spectral line list in the 5550-6236 cm range

A methane spectral line list for the 5550-6236 cm⁻¹ range with the intensity cut off 4×10⁻²⁶ cm/molecule at 296 K is presented. The line list is based on new extensive measurements of methane spectral line parameters performed at different temperatures and pressures of methane and buffer gases N₂, O₂ and air. This spectral line list is prepared in HITRAN-2008 format and contains the following spectral line parameters of about 11,000 lines: position, intensity, energy for lower state (where possible), air-broadening and air-shifting coefficients, exponent of temperature dependence of air-broadening coefficient and self-broadening coefficient.