Search

UNKNOWN

In this study we report the first experimental measurements of air-broadening and air-induced pressure-shift coefficients for approximately 378 transitions in the nu2 fundamental band of CH3D. These results were obtained from analysis of 17 room temperature laboratory absorption spectra recorded at 0.0056 cm(exp -1) resolution using the McMath-Pierce Fourier transform spectrometer located on Kitt Peak, Arizona. Three absorption cells with path lengths of 10.2, 25 and 150 cm were used to record the spectra. The total sample pressures ranged from 0.129x10(exp -2) to 52.855x10(exp -2) atm with CH3D volume mixing ratios of approximately 0.0109 in air. The spectra were analyzed using a multispectrum non-linear least-squares fitting technique. We report measurements for air pressure-broadening coefficients for transitions with quantum numbers as high as J" = 20 and K = 15, where K" = K' equivalent to K (for a parallel band). The measured air broadening coefficients range from 0.0205 to 0.0835 cm(exp -1) atm(exp -1) at 296 K. All the measured pressure-shift coefficients are negative and are found to vary from about -0.0005 to -0.0080 cm(exp -1) atm(exp -1) at the temperature of the spectra. We have examined the dependence of the measured broadening and shift parameters on the J" and K quantum numbers and also developed empirical expressions to describe the broadening coefficients in terms of m (m = -J", J" and J" + 1 in the (sup Q)P- (sup Q)Q-, and (sup Q)R-branch, respectively) and K. On average, the empirical expressions reproduce the measured broadening coefficients to within 4.4%.

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.

High quality and precise measurements of self-broadened and self-shift coefficients in the fundamental band of C-12O-16 were made using spectra recorded at room temperature with the high-resolution (0.0027 cm(exp -1)) McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory on Kitt Peak, Arizona. The spectral region under investigation (2008-2247 cm(exp -1)) contains the P(31) to R(31) transitions. The data were obtained using a high-purity natural isotopic sample ofcarbon monoxide and two absorption cells with pathlengths of 4.08 and 9.98 cm, respectively. Various pressures of CO were used, ranging between 0.25 and 201.2 Torr. The results were obtained by analyzing five spectra simultaneously, using a multispectrum nonlinear least-squares fitting technique. The self-broadened coefficients ranged from 0.0426(2) cm(exp -1) atm(exp -1) at 296 K to 0.0924(2) cm(exp -1) atm(exp -1) at 296 K, while the pressure-induced shift coefficients varied between -0.0042(3) cm(exp -1) atm(exp -1) at 296 K and +0.0005(l) cm(exp -1) atm(exp -1) at 296 K. The value in parentheses is the estimated uncertainty in units of the last digit. The self-broadened coefficients of lines with same values of m in the P and R branches agree close to within experimental uncertainties while the self-shift coefficients showed considerable variation within and between the two branches. The mean value of the ratios of P branch to R branch self-broadened coefficients was found to be 1.01 with a standard deviation of + or - 0.01. Comparisons of the results with other published data were made.

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.

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.

Lorentz-broadening coefficients and pressure-induced line-shift coefficients of 34 individual lines have been determined for the P(40) to R(40) vibration-rotation transitions in the nu(3) fundamental of CO2 using N2 as the buffer gas. The parameters were derived from 0.01/cm resolution infrared absorption spectra recorded using the McMath Fourier transform spectrometer and a nonlinear, least-squares fitting algorithm. It is concluded that the N2-broadening coefficients obtained in the present study agree well with recent high resolution measurements. The results are considered to be of importance not only for predicting the infrared spectrum of the atmosphere due to CO2 absorption or emission but also for verifying theoretical calculations.

Lorentz air-broadening coefficients and relative intensities have been measured for forty-three lines in the pure rotational band and twenty lines in the nu2 band of H2O-16 between 800 and 1150/cm. The results were derived from analysis of nine 0.017/cm-resolution atmospheric absorption spectra recorded over horizontal paths of 0.5-1.5 km with the McMath Fourier transform spectrometer and main solar telescope operated on Kitt Peak by the National Solar Observatory. A nonlinear least-squares spectral fitting technique was used in the spectral analysis. The results are compared with previous measurements and calculations. In most cases, the measured pressure-broadening coefficients and intensities are significantly different from the values in the 1986 HITRAN line parameters compilation.

A complete update of spectroscopic line parameters for the 10-micron bands of ozone is reported. The listing contains calculated positions, intensities, lower state energies, and air- and self-broadened halfwidths of more than 53,000 lines. The results have been generated using improved spectroscopic parameters obtained in a number of recent high resolution laboratory studies. A total of eighteen bands of (O-16)3 (sixteen hot bands plus the nu(1) and nu(3) fundamentals) are included along with the nu(1) and nu(3) fundamentals of both (O-16)(O-16)(O-18) and (O-16)(O-18)(O-16). As shown by comparisons of line-by-line simulations with 0.003/cm resolution balloon-borne stratospheric solar spectra, the new parameters greatly improve the accuracy of atmospheric calculations in the 10-micron region, especially for the isotopic (O-16)(O-16)(O-18) and (O-16)(O-18)(O-16) lines.

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.

The objective is the comprehensive analysis of high resolution atmospheric spectra recorded in the middle-infrared region to obtain simultaneous measurements of coupled parameters (gas concentrations of key trace constituents, total column amounts, pressure, and temperature) in the stratosphere and upper troposphere. Solar absorption spectra recorded at 0.002 and 0.02 cm exp -1 resolutions with the University of Denver group's balloon-borne, aircraft borne, and ground-based interferometers and 0.005 to 0.01 cm exp -1 resolution solar spectra from Kitt Peak are used in the analyses.

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.