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Brown, L. R.

Publications and source records attributed to Brown, L. R..

At least 19 records

Preliminary Modeling of CH3D From 4000 to 4550 cm (exp-1)

A new study of 12CH3D line positions and intensities was performed for the upper portion of the Enneadecad polyad between 4000 and 4550/cm. For this, FTIR spectra were recorded with D-enriched methane samples (at 80 K with a Bruker 125 IFS at 0.005/cm resolution and at 291 K with the McMath-Pierce FTS at 0.011/cm resolution, respectively). Line positions and intensities were retrieved by least square curve-fitting procedures and analyzed using the effective Hamiltonian and the effective dipole moment expressed in terms of irreducible tensor operators adapted to symmetric top molecules. Initially, only the cold spectrum was used to identify quantum assignments and predict 12CH3D relative intensities in this region. To assign higher quanta up to J equal 14, additional line positions and intensities were obtained from two room temperature spectra. In the final stage, measured intensities from both the cold and the room temperature data were normalized to corresponding values at 296 K and then averaged. Combining the two temperature datasets confirmed the assumed quantum assignments and also demonstrated the relative accuracies to be better than 70.0002/cm for line positions and at least +/-6% for intensities so that approx.1160 features were selected. Including additional assignments from the room temperature spectra alone permitted 1362 line intensities of 11 bands (involving 23 vibrational symmetry components) to be reproduced with an RMS of 9%. Over 4085 selected positions for 12 bands were modeled to 0.008/cm. Nevertheless a number of known assignments could not be modeled to within our experimental precisions. More work is needed to obtain a complete characterization of this complex polyad.

Nikitin, A. V.

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

Cryogenic Absorption Cells Operating Inside a Bruker IFS-125HR: First Results for 13CH4 at 7 Micrometers

New absorption cells designed specifically to achieve stable temperatures down to 66 K inside the sample compartment of an evacuated Bruker IFS-125HR Fourier transform spectrometer (FTS) were developed at Connecticut College and tested at the Jet Propulsion Laboratory (JPL). The temperature stabilized cryogenic cells with path lengths of 24.29 and 20.38 cm were constructed of oxygen free high conductivity (OFHC) copper and fitted with wedged ZnSe windows using vacuum tight indium seals. In operation, the temperature-controlled cooling by a closed-cycle helium refrigerator achieved stability of 0.01 K. The unwanted absorption features arising from cryodeposits on the cell windows at low temperatures were eliminated by building an internal vacuum shroud box around the cell which significantly minimized the growth of cryodeposits. The effects of vibrations from the closed-cycle helium refrigerator on the FTS spectra were characterized. Using this set up, several high-resolution spectra of methane isotopologues broadened with nitrogen were recorded in the 1200-1800 per centimeter spectral region at various sample temperatures between 79.5 and 296 K. Such data are needed to characterize the temperature dependence of spectral line shapes at low temperatures for remote sensing of outer planets and their moons. Initial analysis of a limited number of spectra in the region of the R(2) manifold of the v4 fundamental band of 13CH4 indicated that an empirical power law used for the temperature dependence of the N2-broadened line widths would fail to fit the observed data in the entire temperature range from 80 to 296 K; instead, it follows a temperature-dependence similar to that reported by Mondelain et al. [17,18]. The initial test was very successful proving that a high precision Fourier transform spectrometer with a completely evacuated optical path can be configured for spectroscopic studies at low temperatures relevant to the planetary atmospheres.

Sung, K.

Exponential Sum Absorption Coefficients of Phosphine from 2750 to 3550/cm for Application to Radiative Transfer Analyses on Jupiter and Saturn

PH3 exponential sum k coefficients were computed between 2750 and 3550/cm (2.82-3.64 (microns), in view of future application to radiative transfer analyses of Jupiter and Saturn in a phosphine absorption band near 3 microns. The temperature and pressure of this data set cover the ranges from 80 to 350 K and from 10 (exp -3)to 10(exp 1) bars, respectively. Transmission uncertainty incurred by the use of the k coefficients is smaller than a few percent as long as the radiation is confined above an altitude of a few bars in the giant planets. In spectral regions of weak absorption at high pressures close to 10 bars, contributions from far wings of strong absorption lines must be carefully taken into account. Our data set helps map the three-dimensional distribution of PH3 on the giant planets, revealing their global atmospheric dynamics extending down to the deep interior. The complete k coefficient data set of this work is available at the Web site of the NASA Planetary Data System Atmospheres Node.

phosphine

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.

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.

Absolute Rovibrational Intensities, Self-Broadening and Self-Shift Coefficients for the X(sup 1) Sigma(+) V=3 (left arrow) V=0 Band (C-12)(O-16)

The rotationless transition moment squared for the x(sup 1) sigma (sup +) v=3 (left arrow) v=0 band of CO is measured to be the absolute value of R (sub 3-0) squared = 1.7127(25)x 10(exp -7) Debye squared. This value is about 8.6 percent smaller than the value assumed for HITRAN 2000. The Herman-Wallis intensity factor of this band is F=1+0.01168(11)m+0.0001065(79)m squared. The determination of self-broadening coefficients is improved with the inclusion of line narrowing; self-shifts are also reported.

Chackerian, Charles, Jr.

Line intensities: the good, the bad and the ugly

Atmospheric remote sensing requires that line intensities be measured and modeled to 5 percent or better in laboratory studies. Successes and failures for analyses of carbon monoxide, methane, methanol and nitric acid will be reviewed.

Spectroscopy

Absolute Rovibrational Intensities for the Chi(sup 1)Sigma(sup +) v=3 <-- 0 Band of (12)C(16)O Obtained with Kitt Peak and BOMEM FTS Instruments

This work was initiated to compare absolute line intensities retrieved with the Kitt Peak FTS (Fourier Transform Spectrometer) and Ames BOMEM FTS. Since thermal contaminations can be a problem using the BOMEM instrument if proper precautions are not taken it was thought that measurements done at 6300 per cm would more easily result in satisfactory intercomparisons. Very recent measurements of the CO 3 <-- 0 band fine intensities confirms results reported here that the intensities listed in HITRAN (High Resolution Molecular Absorption Database) for this band are on the order of six to seven percent too low. All of the infrared intensities in the current HITRAN tabulation are based on the electric dipole moment function reported fifteen years ago. The latter in turn was partly based on intensities for the 3 <-- 0 band reported thirty years ago. We have, therefore, redetermined the electric dipole moment function of ground electronic state CO.

Chackerian, Charles, Jr.

Positions and Intensities in the 2v4/v1/v3 Vibrational System of 14NH3 near 3 mu m

Line positions and line intensities of the v1, v3 and 2V4 bands of 14NH3 were analyzed using line positions from 0.0054 cm-1 apodized resolution FT spectra recorded at Orsay and using line intensities from 0.011 cm-1 unapodized resolution FT spectra recorded at Kitt peak National Observatory. The theoretical model and the set of programs developed for treating the infrared system v1/v3/2v4 of ammonia are briefly discussed.

ammonia Jupiter infrared mapping