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At least 73 records · Page 4

DIAL with heterodyne detection including speckle noise: Aircraft/shuttle measurements of O3, H2O, and NH3 with pulsed tunable CO2lasers

A parametric analysis of DIAL sensitivity with heterodyne detection is presented and comparisons with direct detection are discussed. Examples are given for monitoring vertical distributions of O3, H2O, and NH3 using a ground-, aircraft-, or shuttle-based pulsed tunable CO2 laser DIAL system. Results indicate that maximum sensitivity at minimum laser energy per measurement requires multiple pulse operation with the energy per pulse selected so that the measured photon rate is approximately equal to the detector IF bandwidth. Measurement sensitivities can be maximized and interference effects minimized by fine adjustment of measurement frequencies using the tunability of high pressure lasers. The use of rare isotope lasers minimizes loss due to CO2 atmospheric absorption.

Brockman, P.↗

DIAL with heterodyne detection including speckle noise: Aircraft/shuttle measurements of O3, H2O, and NH3 with pulsed tunable CO2 lasers

Atmospheric trace constituent measurements with higher vertical resolution than attainable with passive radiometers are discussed. Infrared differential absorption lidar (DIAL), which depends on Mie scattering from aerosols, has special advantages for tropospheric and lower stratospheric applications and has great potential importance for measurements from shuttle and aircraft. Differential absorption lidar data reduction involves comparing large amplitude signals which have small differences. The accuracy of the trace constituent concentration inferred from DIAL measurements depends strongly on the errors in determining the amplitude of the signals. Thus, the commonly used SNR expression (signal divided by noise in the absence of signal) is not adequate to describe DIAL measurement accuracy and must be replaced by an expression which includes the random coherent (speckle) noise within the signal. A comprehensive DIAL computer algorithm is modified to include heterodyne detection and speckle noise. Examples for monitoring vertical distributions of O3, H2O, and NH3 using a ground-, aircraft-, or shuttle-based pulsed tunable CO2 laser DIAL system are given.

Brockman, P.↗

Absorption coefficients of solid NH3 from 50 to 7000 per cm

Thin-film spectra of solid NH3 at a resolution of 1 per cm were used to determine its absorption coefficient over the range 50-7000 per cm. The thin films were formed inside a liquid N2 cooled dewar using a variety of substrates and dewar windows. The spectra were recorded with two Fourier spectrometers, one covering the range from 1 to 4 microns and the other from 2.6 to 200 microns. The thickness of the films was measured with a laser interference technique. The absorption coefficients were determined by application of Lambert's law and by a fitting procedure to the observed spectra using thin-film theory. Good agreement was found with the absorption coefficients recently determined by other investigators over a more restricted wavelength range. A metastable phase was observed near a temperature of 90 K and its absorption coefficient is reported. No other major spectral changes with temperature were noted for the range 88-120 K.

Sill, G.↗

Far-UV, visible, and near-IR reflectance spectra of frosts of H2O, CO2, NH3 and SO2

Measurements in the 0.1-2.5 micron range are presented for the reflectance spectra of the frosts of several volatiles pertinent to the study of comet nuclei. The frost spectra have distinctive features permitting their identification by spectroscopic reflectance remote sensing, notably in the far UV. It is found that: (1) H2O has a minimum at 0.16 microns and a maximum at 0.13 microns; (2) CO2 has minima near 0.21, 0.18 and 0.125 microns, with maxima at 0.19, 0.135 and 0.120 microns; (3) NH3 is bright at wavelengths longer than 0.21 microns, where reflectance drops to a value of only a few per cent at shorter wavelengths; (4) SO2 has a sharp drop at 0.32 microns, with a minimum at 0.18 microns and a maximum at 0.13 microns. The features in the frost spectra largely correspond to absorption line bands in the gas phase.

Hapke, B.↗

Photolysis of CH4-NH3 mixtures and PH3 as models for the photochemical transformations on the primitive earth and Jupiter

Methane, ammonia and phosphine are some of the possible constituents of the atmospheres of the Jovian planets and their satellites. Photolysis of NH3 in the presence of CH4 at 185 nm in the temperature range of 25 C to -100 C results in the decomposition of CH4. The reaction is inhibited by added H2 or SF6. These findings are consistent with the reaction of hot hydrogen atoms with CH4 to give the CH3 radical. P2H4 is the initial product formed by the photolysis of PH3 at 206 nm. Kinetic studies established that it is the intermediate in the formation of P4 from PH3. The potential significance of these reactions to the atmospheric photochemistry of the Jovian planets and moons is discussed.

Ferris, J. P.↗

A theoretical investigation of gaseous absorption by water droplets from SO2-HNO3-NH3-CO2-HCl mixtures

A physical-chemical model is developed and used to investigate gaseous absorption by water droplets from trace gas mixtures. The model is an extension of that of Carmichael and Peters (1979) and includes the simultaneous absorption of SO2, NH3, HNO3, CO2, and HCl. Gas phase depletion is also considered. Presented results demonstrate that the absorption behavior of raindrops is strongly dependent on drop size, fall distance, trace gas concentrations, and the chemical and physical properties of the constituents of the mixture. In addition, when gas phase depletion is considered, the absorption rates and equilibrium values are also dependent on the precipitation rate itself. Also, the trace constituents liquid phase concentrations may be a factor of six or more lower when gas depletion is considered then when the depletion is ignored. However, the hydrogen ion concentration may be insensitive to the gas phase depletion.

Adewuyi, Y. G.↗

Spectroscopic line parameters of NH3 and PH3 in the far infrared

NH3 and PH3 rotation and rotation-inversion line parameters in the far to medium IR are calculated for remote sounding purposes of planetary atmospheres; 1607 lines of (N-14)H3, 362 lines of (N-15)H3 and 325 lines of PH3 are compiled. The absolute intensity formulation has been reviewed in the case of rotation and rotation-inversion lines of molecules with C(3v) symmetry. The justification for the general agreement between the authors, and comparisons with other published expressions are given.

Husson, N.↗

The design and technology development for A 150 mlb resistojet for H2 or NH3

A 150 mlb thrust level hybrid resistojet which may operate on either H2 or NH3 is described whose design technique allows temperature distribution forecasting by means of a microcomputer-implemented mathematical model. The longer computer run times that accompany the exclusive use of BASIC, relative to assembled languages, are offset by the flexibility offered and the reduction of reprogramming and debugging efforts. The integration of a compact first-stage coiled heater with a concentric tubular gas heater offers direct matching of the 28 V terminal of the spacecraft system, while keeping maximum heater wall temperatures to less than 60 K over that of the gas temperature at the throat. Among the novel materials employed are grain-stabilized rhenium for heating elements and high purity aluminas for insulators.

Page, R. J.↗

M dependence in the analysis of NH3-He microwave double resonance experiments

New close-coupled calculations of laboratory-frame, m-dependent cross sections for rotational excitation in NH3-He collisions are used to examined the validity of using degeneracy averaged values in the analysis of four-level double resonance experiments. It is found that the proper use of m-dependent cross sections and absorption probabilities produces only minor changes in the calculated Delta I/I (the fractional change in the signal absorption intensity when pumping radiation is applied) and does not, therefore, resolve the discrepancies between theoretical and experimental values that were noted in previous studies.

Davis, S. L.↗

Nitriding of titanium and its alloys by N2, NH3 or mixtures of N2 + H2 in a dc arc plasma at low pressures ( or = to torr)

The dc glow discharges in different gas mixtures of Ar + N2, Ar + NH3 or Ar + N2 + H2 result in the surface nitriding of Ti metal and its alloy (Ti6Al4V). Various gas mixtures were used in order to establish the main active species governing the nitriding process, i.e., N, N2, NH, or NH2 as excited or ionized particles. The dc discharge was sampled and analyzed by quadruple mass spectrometry (QPMS) and optical emission spectroscopy (OES), and the nitrided samples were analyzed by scanning electron microscopy (SEM) with an EDAX attachment, microhardness, and Fourier transform infrared reflectance spectrometry (FTIR). It was found that the excited and ionized nitrogen and hydrogen atoms are the main species responsible for the nitriding process in a dc glow discharge.

Avni, R.↗

Comparison of the frequencies of NH3, CO2, H2O, N2O, CO, and CH4 as infrared calibration standards

The absolute accuracies of infrared calibration standards for the line positions have been investigated using a 0.0056-kayser-resolution (unapodized) Fourier-transform spectrum recorded from 550 to 5000 kayser. The spectrum has been obtained using a multicell arrangement containing the various molecular species. Detailed comoparisons reveal that standards for CO2, CH4, and N2O obtained from laser research and NH3 from Fourier-transform spectrometer research are consistent within the accuracies of the present data (+ or 0.0001 kayser). However, certain N2O, H2O, and CO values in the 1100-to 2300 kayser region are systematically high by 0.0001 to 0.0004 kayser. Correction factors for the H2O and CO standards are obtained to bring these into agreement with the laser values. In addition, corrected values for the 2nu-2 and nu-1 bands of N2O at 9 microns are reported.

Brown, L. R.↗

Photolysis products of CO, NH3 aND H2O and their significance to reactions on interstellar grains

With the increase in evidence that interstellar grains are the basic building blocks of comets and with the realization that comet collisions with the earth have probably occured at a much higher frequency than earlier assumed it may be presumed that interstellar dust chemistry played an important role in the early chemistry of the earth. As a part of the study of the photochemical processes taking place on interstellar grains the photolysis of mixtures of CO, NH3 and H2O was performed at 10 K, 77K and 298K. The reaction products were determined by GC/MS and HPLC analysis to be lactic acid, glycolic acid, hydroxyacetamide, urea, biuret, oxamic acid, oxamide, glyceric acid and glyceramide. Ethylene glycol and glycerol were also detected but is is not clear at present whether these are true photoproducts or contaminants. The mechanism of formation of these molecules are discussed as well as their possible significance to the origins of life.

Ferris, J. P.↗

Photochemical reactions in interstellar grains photolysis of CO, NH3, and H2O

The interstellar grains are currently considered to be the basic building blocks of comets and, possibly, meteorites. To test this theory, a simulation of the organic layer accreted onto interstellar dust particles was prepared by slow deposition of a CO:NH3:H2O gas mixture on an Al block at 10 K, with concomitant irradiation with vacuum UV. The results of the HPLC and IR analyses of the nonvolatile residue formed by photolysis at 10 K are compared with those observed at 77 K and 298 K. Some of the compounds that may be present on the surfaces of interstellar dust particles have been identified, and some specific predictions concerning the types of molecular species present in comets could be drawn. The results also suggest that photochemical reactions may have been important for the formation of meteorite components. The implication of the findings to the questions of the source of organic matter on earth and the origin of life are discussed.

Agarwal, V. K.↗

Parametrization of electron impact ionization cross sections for CO, CO2, NH3 and SO2

The electron impact ionization and dissociative ionization cross section data of CO, CO2, CH4, NH3, and SO2, measured in the laboratory, were parameterized utilizing an empirical formula based on the Born approximation. For this purpose an chi squared minimization technique was employed which provided an excellent fit to the experimental data.

Srivastava, Santosh K.↗

Studies of elastic e-NH3 collisions

Differential and momentum-transfer cross sections for the elastic scattering of electrons by NH3 have been obtained for collision energies of between 2.5 and 20 eV using the fixed-nuclei static-exchange approximation of the Schwinger variational principle. At intermediate and large scattering angles, good agreement is found between calculated and relative experimental cross sections. The differential cross sections reveal evidence of a weak d-wave enhancement around 8 eV.

Pritchard, H. P.↗

Laboratory measurements of the 7.5-9.38-mm absorption of gaseous ammonia (NH3) under simulated Jovian conditions

An attempt is made to infer the abundance and distribution of ammonia from RF emission measurements more accurately than heretofore, on the basis of the results of laboratory measurements for the mm-wave opacity of gaseous ammonia under simulated Jovian atmosphere conditions. The measurements were conducted at various frequencies in the 32-40 GHz range at 2 atm and 203 K; the atmospheric mixture was 88.34 percent H2, 9.81 percent He, and 1.85 percent NH3. Experimental results are found to be readily modeled by the Gross (1955) line-shape factor, rather than that of Van Vleck and Weisskopf (1945).

Joiner, Joanna↗

The binding energies of Cu(+)-(H2O)n and Cu(+)-(NH3)n (n = 1-4)

The successive binding energies of up to four H2O and NH3 ligands to Cu(+) are computed at the self-consistent-field and modified coupled-pair functional levels. The most stable structures are those where all ligands are equivalent. Replacing Cu(+) by a point charge gives binding energies that are in good agreement with ab initio and experimental results, and is consistent with bonding that is largely charge dipole in nature. About two-thirds of the large reduction in ligand binding energy between the second and third ligand is due to ligand-ligand repulsion, while one-third is due to increased metal-ligand repulsion resulting from a loss of sd-sigma hybridization. The first and second ligand binding energies increase substantially at the correlated level due to an improved description of sd-sigma hybridization.

Bauschlicher, Charles W., Jr.↗

A theoretical study of the positive and dipositive ions of M(NH3)n and M(H2O)n for M = Mg, Ca, or Sr

The structure and binding energies are determined for many of the M(H2O)n(+) and M(H2O)n(2+) species, for n = 1-3 and M = Mg, Ca, or Sr. The trends are explained in terms of metal sp or sd-sigma hybridization and core polarization. The M(NH3)n(+) systems, with M = Mg or Sr, are also studied. For the positive ions, the low-lying excited states are also studied and compared with experiment. The calculations suggest an alternative interpretation of the SrNH3(+) spectrum.

Bauschlicher, Charles W., Jr.↗