Progress in the measurement on temperature-dependence of H2-broadening of cold and hot CH4
UNKNOWN
Smith, Mary Ann H.↗
Engineering topics
Devi, V. Malathy
Publications and source records attributed to Devi, V. Malathy.
Self- and Air-Broadened Line Shapes in the 2v3 P and R Branches of 12CH4
In this paper we report line shape parameters of 12CH4 for several hundred 2V(sub 3) transitions in the spectral regions 5891-5996 cm( exp -1) (P branch) and 6015-6115 cm(exp -1) (R branch). Air- and self-broadening coefficients were measured as a function of temperature; line mixing via off-diagonal relaxation matrix element coefficients was also obtained for 47 transition pairs. In total, nearly 1517 positions and intensities were retrieved, but many transitions were too weak for the line shape study. For this analysis, we used 25 high-resolution (0.0056 and 0.0067 cm(ex[ -1) and high signal-to-noise (S/N) spectra of high-purity 12CH4 and the same high-purity 12CH4 broadened by dry air recorded at different sample temperatures between 130 K and 295 K with the Bruker IFS 125HR Fourier transform spectrometer at JPL. Three different absorption cells were used (1) a White cell set to a path length of 13.09 m for room temperature data, (2) a single-pass 0.2038 m long coolable cell (for self-broadening) and (3) a multipass cell with 20.941 m total path coolable Herriott cell (for air-broadening). In total there were 13 spectra with pure 12CH4 (0.27-599 Torr) and 12 air-broadened spectra with total sample pressures of 80-805 Torr and volume mixing ratios (VMR) of methane between 0.18 and 1.0. An interactive multispectrum nonlinear least-squares technique was employed to fit the individual P10-P1 and R0-R10 manifolds in all the spectra simultaneously. Results obtained from the present analysis are compared to other recent measurements.
Devi, V. Malathy↗
Air- and Self-Broadened Half Widths, Pressure-Induced Shifts, and Line Mixing in the Nu(sub 2) Band of (12)CH4
Lorentz self- and air-broadened half width and pressure-induced shift coefficients and their dependences on temperature have been measured from laboratory absorption spectra for nearly 130 transitions in the nu(sub 2) band of (12)CH4. In addition line mixing coefficients (using the relaxation matrix element formalism) for both self- and airbroadening were experimentally determined for the first time for a small number of transitions in this band. Accurate line positions and absolute line intensities were also determined. These parameters were obtained by analyzing high-resolution (approx. 0.003 to 0.01 per cm) laboratory spectra of high-purity natural CH4 and air-broadened CH4 recorded at temperatures between 226 and 297 K using the McMath-Pierce Fourier transform spectrometer (FTS) located at the National Solar Observatory on Kitt Peak, Arizona. A multispectrum nonlinear least squares technique was used to fit short (5-15 per cm) spectral intervals in 24-29 spectra simultaneously. Parameters were determined for nu(sub 2) transitions up to J" = 16. The variations of the measured broadening and shift parameters with the rotational quantum number index and tetrahedral symmetry species are examined. The present results are also compared with previous measurements available in the literature.
Smith, M. A. H.↗
Spectral Line Parameters Including Temperature Dependences of Self- and Air-Broadening in the 2 (left arrow) 0 Band of CO at 2.3 micrometers
Temperature dependences of pressure-broadened half-width and pressure-induced shift coefficients along with accurate positions and intensities have been determined for transitions in the 2<--0 band of C-12 O-16 from analyzing high-resolution and high signal-to-noise spectra recorded with two different Fourier transform spectrometers. A total of 28 spectra, 16 self-broadened and 12 air-broadened, recorded using high- purity (greater than or equal to 99.5% C-12-enriched) CO samples and CO diluted with dry air(research grade) at different temperatures and pressures, were analyzed simultaneously to maximize the accuracy of the retrieved parameters. The sample temperatures ranged from 150 to 298K and the total pressures varied between 5 and 700 Torr. A multispectrum nonlinear least squares spectrum fitting technique was used to adjust the rovibrational constants (G, B, D, etc.) and intensity parameters (including Herman-Wallis coefficients), rather than determining individual line positions and intensities. Self-and air-broadened Lorentz half-width coefficients, their temperature dependence exponents, self- and air-pressure-induced shift coefficients, their temperature dependences, self- and air-line mixing coefficients, their temperature dependences and speed dependence have been retrieved from the analysis. Speed-dependent line shapes with line mixing employing off-diagonal relaxation matrix element formalism were needed to minimize the fit residuals. This study presents a precise and complete set of spectral line parameters that consistently reproduce the spectrum of carbon monoxide over terrestrial atmospheric conditions.
Devi, V. Malathy↗
Room-temperature Broadening and Pressure-shift Coefficients in the nu(exp 2) Band of CH3D-O2: Measurements and Semi-classical Calculations
We report measured Lorentz O2-broadening and O2-induced pressure-shift coefficients of CH3D in the nu(exp 2) fundamental band. Using a multispectrum fitting technique we have analyzed 11 laboratory absorption spectra recorded at 0.011 cm(exp 1) resolution using the McMath-Pierce Fourier transform spectrometer, Kitt Peak, Arizona. Two absorption cells with path lengths of 10.2 and 25 cm were used to record the spectra. The total sample pressures ranged from 0.98 to 339.85 Torr with CH3D volume mixing ratios of 0.012 in oxygen. We report measurements for O2 pressure-broadening coefficients of 320 nu(exp 2) transitions with quantum numbers as high as J0(sup w) = 17 and K = 14, where K(sup w) = K' is equivalent to K (for a parallel band). The measured O2-broadening coefficients range from 0.0153 to 0.0645 cm(exp -1) atm(exp -1) at 296 K. All the measured pressure-shifts are negative. The reported O2-induced pressure-shift coefficients vary from about -0.0017 to -0.0068 cm(exp -1) atm(exp -1). We have examined the dependence of the measured broadening and shift parameters on the J(sup W), and K quantum numbers and also developed empirical expressions to describe the broadening coefficients in terms of m (m = -J(sup W), J(sup W), and J(sup w) + 1 in the QP-, QQ-, and QR-branch, respectively) and K. On average, the empirical expressions reproduce the measured broadening coefficients to within 4.4%. The O2-broadening and pressure shift coefficients were calculated on the basis of a semiclassical model of interacting linear molecules performed by considering in addition to the electrostatic contributions the atom-atom Lennard-Jones potential. The theoretical results of the broadening coefficients are generally larger than the experimental data. Using for the trajectory model an isotropic Lennard-Jones potential derived from molecular parameters instead of the spherical average of the atom-atom model, a better agreement is obtained with these data, especially for |m| <= 12 values (11.3% for the first calculation and 8.1% for the second calculation). The O2-pressure shifts whose vibrational contribution are either derived from parameters fitted in the QQ-branch of selfinduced shifts of CH3D or those obtained from pressure shifts induced by Xe in the nu(sup 3) band of CH3D are in reasonable agreement with the scattered experimental data (17.0% for the first calculation and 18.7% for the second calculation).
Predoi-Cross, Adriana↗
Line Mixing in Water Vapor and Methane
A multispectrum fitting algorithm has been used to identify line mixing and determine mixing parameters for infrared transitions of H2O and CH4 in the 5-9 micrometer region. Line mixing parameters at room temperature were determined for two pairs of transitions in the v2 fundamental band of H2O-16, for self-broadening and for broadening by H2, He, CO2, N2, O2 and air. Line mixing parameters have been determined from air-broadened CH4 spectra, recorded at temperatures between 210 K and 314 K, in selected R-branch manifolds of the v4 band. For both H2O and CH4, the inclusion of line mixing was seen to have a greater effect on the retrieved values of the line shifts than on the retrieved values of other parameters
Smith, M. A. H.↗
Temperature-Dependence of Air-Broadened Line Widths and Shifts in the nu3 Band of Ozone
The 9.6-micron bands of O3 are used by many remote-sensing experiments for retrievals of terrestrial atmospheric ozone concentration profiles. Line parameter errors can contribute significantly to the total errors in these retrievals, particularly for nadir-viewing. The McMath-Pierce Fourier transform spectrometer at the National Solar Observatory on Kitt Peak was used to record numerous high-resolution infrared absorption spectra of O3 broadened by various gases at temperatures between 160 and 300 K. Over 30 spectra were analyzed simultaneously using a multispectrum nonlinear least squares fitting technique to determine Lorentz air-broadening and pressure-induced shift coefficients along with their temperature dependences for selected transitions in the 3 fundamental band of (16)O3. We compare the present results with other measurements reported in the literature and with the ozone parameters on the 2000 and 2004 editions of the HITRAN database.
Smith, Mary A. H.↗
Air-Broadening of H2O as a Function of Temperature: 696 - 2163 cm(exp -1)
The temperature dependence of air-broadened halfwidths are reported for some 500 transitions in the (000)-(000) and (010)-(000) bands of H2(16)O using gas sample temperatures ranging from 241 to 388 K. These observations were obtained from infrared laboratory spectra recorded at 0.006 to 0.011 cm(exp-1) resolution with the McMath-Pierce Fourier transform spectrometer located at Kitt Peak. The experimental values of the temperature dependence exponents, eta, were grouped into eight subsets and fitted to empirical functions in a semi-global procedure. Overall, the values of eta were found to decrease with increasing rotational quantum number J. The number of measurements (over 2200) and transitions (586) involved exceeds by a large margin that of any other comparable reported study.
Toth, R. A.↗
Air- and N2-Broadening Coefficients and Pressure-Shift Coefficients in the C-12(O2-16) Laser Bands
In this paper we report the pressure broadening and the pressure-induced line shift coefficients for 46 individual rovibrational lines in both the (12)C(16)O2, 00(sup 0)1-(10(sup 0)0-02(sup 0)0)I, and 00(sup 0)1-(10(sup 0)0-02(sup 0)0)II, laser bands (laser band I centered at 960.959/cm and laser band II centered at 1063.735/cm) determined from spectra recorded with the McMath-Pierce Fourier transform spectrometer. The results were obtained from analysis of 10 long-path laboratory absorption spectra recorded at room temperature using a multispectrum nonlinear least-squares technique. Pressure effects caused by both air and nitrogen have been investigated. The air-broadening coefficients determined in this study agree well with the values in the 1996 HITRAN database; ratios and standard deviations of the ratios of the present air-broadening measurements to the 1996 HITRAN values for the two laser bands are: 1.005(15) for laser band I and 1.005(14) for laser band II. Broadening by nitrogen is 3 to 4% larger than that of air. The pressure-induced line shift coefficients are found to be transition dependent and different for the P- and R-branch lines with same J" value. No noticeable differences in the shift coefficients caused by air and nitrogen were found. The results obtained are compared with available values previously reported in the literature.
Devi, V. Malathy↗
Pressure Broadening and Pressure Shift Coefficients in the 2nu(sup 0, sub 2) and nu(sub 1) Bands of (16)O(13)C(18)O
In this study we report the first measurements of the pressure broadening and the pressure-induced line shift coefficients due to air and nitrogen for 93 individual rovibrational lines, P(46) to R(46) and P(50) to R(45), respectively, belonging to the 2nu(sup 0, sub 2) and nu(sub 1) bands of (16)O(13)C(18)O. The results were obtained by analyzing ten long path, high-resolution laboratory, absorption spectra using a multispectrum nonlinear least-squares technique. Broadening due to nitrogen was about 4% larger than by air. Similar to broadening coefficients, the pressure-shift coefficients were found to be transition dependent, but different for the P- and R-branch lines with the same rotational quantum number, J. Except for a few R-branch lines, the measured shift coefficients were negative. The shift coefficients varied from + 4 x 10(exp -3)/cm.atm at 296 K to -5.6 x 10(exp -3)/cm.atm at 296 K. Comparisons of the broadening and shift coefficients between the two bands, between the P and R branches, and between the two broadening gases are reported. No significant difference between shift coefficients of the two bands or the two broadening gases was observed. The results obtained were compared with those reported in the literature for the more abundant (12)C(16)O2 species.
Devi, V. Malathy↗
Spectroscopic Parameters for Ozone and its Isotopes: Current Status, Prospects for Improvement, and the Identification of 16O16O17O and O-16O-16O-17 and O-16O-17O-16 Lines in Infrared Ground-Based and Stratospheric Solar Absorption Spectra
We describe the updates to the spectroscopic parameters of ozone and its isotopes in the 1996 HITRAN compilation. Recent published studies not included in HITRAN are also summarized. Finally, we report the identification of infrared lines of the v(sub 3) bands of O-16O-16O-17 and O-16O-17O-16 in high-resolution solar spectra recorded by stratospheric balloon-borne and ground-based Fourier transform spectrometers.
Rinsland, C. P.↗
Absolute Rovibrational Intensities of C-12O2-16 Absorption Bands in the 3090-3850/ CM Spectral Region
A multispectrum nonlinear least-squares fitting technique has been used to determine the absolute intensities for approximately 1500 spectral lines in 36 vibration - rotation bands Of C-12O2-16 between 3090 and 3850/ cm. A total of six absorption spectra of a high- purity (99.995% minimum) natural sample of carbon dioxide were used in the analysis. The spectral data (0.01/cm resolution) were recorded at room temperature and low pressure (1 to 10 Torr) using the McMath-Pierce Fourier transform spectrometer of the National Solar Observatory (NSO) on Kitt Peak. The absorption path lengths for these spectra varied between 24.86 and 385.76 m. The first experimental determination of the intensity of the theoretically predicted 2(nu)(sub 2, sup 2) + nu(sub 3) "forbidden" band has been made. The measured line intensities obtained for each band have been analyzed to determine the vibrational band intensity, S(sub nu), in /cm/( molecule/sq cm) at 296 K, square of the rotationless transition dipole moment |R|(exp 2) in Debye, as well as the nonrigid rotor coefficients. The results are compared to the values listed in the 1996 HITRAN database which are obtained using the direct numerical diagonalization (DND) technique as well as to other published values where available.
Devi, V. Malathy↗
Temperature dependence of Lorentz air-broadening and pressure-shift coefficients of (12)CH4 lines in the 2.3-micron spectral region
High-resolution (0.01/cm) absorption spectra of lean mixtures of CH4 in dry air were recorded with the McMath-Pierce Fourier transform spectrometer (FTS) of the National Solar Observatory on Kitt Peak at various temperatures between 24 and -61 C. The spectra have been analyzed to determine the values at room temperature of pressure-broadened widths and pressure-induced shifts of more than 740 transitions. The temperature dependence of air-broadened widths and pressure-induced shifts was deduced for approx. 370 transitions in the nu(sub 1) + nu(sub 4), nu(sub 3) + nu(sub 4), and nu(sub 2) + nu(sub 3) bands of (12)CH4 located between 4118 and 4615/cm. These results were obtained by analyzing a total of 29 spectra simultaneously using a multi-spectral non-linear least-squares fitting technique. This new technique allowed the determination of correlated spectral line parameters (e.g. intensity and broadening coefficient) better than the procedure of averaging values obtained by fitting the spectra individually. This method also provided a direct determination of the uncertainties in the retrieved parameters due to random errors. For each band analysed in this study the dependence of the various spectral line parameters upon the tetrahedral symmetry species and the rotational quantum numbers of the transitions is also presented.
Devi, V. Malathy↗
The 2nu2 + nu3 and 2nu2 + nu1 bands of (O-16)3 at 4.1 microns - Line positions and intensities
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Rinsland, Curtis P.↗
Line parameters for ozone hot bands in the 4.8-micron spectral region
Line positions, intensities, and lower-state energies have been calculated for nine hot bands of (O-16)3 in the 4.8-micron spectral region using improved spectroscopic parameters deduced in recent high-resolution laboratory studies. The good quality of the hot-band parameters has been verified through comparisons of line-by-line simulations with 0.005/cm-resolution laboratory spectra of ozone. The present work and the line parameters calculated for the main bands by Pickett et al. (1988) provide a complete update of ozone spectroscopic parameters in the 4.8 micron region.
Camy-Peyret, Claude↗
High resolution spectroscopy to support atmospheric measurements
Detailed knowledge of the molecular spectra of ozone and other infrared-active atmospheric species is needed for accurate calculation of atmospheric heating and cooling rates in climate models. Remote sensing experiments on the Nimbus-7 satellites and the Spacelab-3 Space Shuttle Mission have shown that space-based measurements of infrared absorption or emission can be used to accurately determine the concentrations and distributions of stratospheric species on a global scale. The objective of this research task is to improve knowledge of the spectroscopic line parameters (positions, intensities, assignments, halfwidths, and pressure-induced shifts) of key atmospheric constituents through laboratory measurements.
Smith, Mary Ann H.↗
Measurements of argon broadened Lorentz width and pressure-induced line shift coefficients in the nu4 band of (C-12)H4
Room temperature argon broadened halfwidth and pressure-induced line shift coefficients have been determined for 118 transitions in the nu4 band of (C-12)H4 from analysis of high resolution laboratory absorption spectra recorded with the McMath Fourier transform spectrometer operated on Kitt Peak by the National Solar Observatory. Transitions up to J-double-prime = 12 have been measured using a nonlinear least-squares spectral fitting procedure. The variation of the measured halfwidth coefficients with symmetry type and rotational quantum number is very similar to that measured previously for N2 and air broadening, but the absolute values of the argon broadening coefficients are all smaller. On average, the ratio of the argon broadened halfwidth coefficient to the corresponding N2 broadened halfwidth coefficient is 0.877 + or - 0.017 (2 Sigma). More than 95 percent of the pressure-induced shifts are negative with values ranging from -0.0081 to +0.0055/cm atm. The pressure shifts in argon are nearly equal to corresponding values measured previously in N2 and air.
Rinsland, Curtis P.↗
Air-broadened Lorentz halfwidths and pressure-induced line shifts in the nu(4) band of C-13H4
Air-broadened halfwidths and pressure-induced line shifts in the nu(4) fundamental of C-13H4 were determined from spectra recorded at room temperature and at 0.01/cm resolution using a Fourier transform spectrometer. Halfwidths and pressure shifts were determined for over 180 transitions belonging to J-double prime values of less than or = to 16. Comparisons of air-broadened halfwidths and pressure-induced line shifts made for identical transitions in the nu(4) bands of C-12H4 and C-13H4 have shown that C-13H4 air-broadened halfwidths are about 5 percent smaller than the corresponding C-12H4 halfwidths, and the pressure shifts for C-13H4 lines are about 5-15 percent larger than those for C-12H4.
Devi, V. Malathy↗