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All sourcesNASA NTRSDOE OSTI
NASA NTRS1991

Cross sections for direct and dissociative ionization of NH3 and CS2 by electron impact

A crossed electron beam-molecular beam collision geometry is used to measure cross sections for the production of positive ions by electron impact on NH3 and CS2. Ionization cross-section data for NH3 and the values of various cross sections are presented, as well as ionization efficiency curves for CS2. Considerable differences are found between the various results on NH3. The present values are close to the data of Djuric et al. (1981). The semiempirical calculations of Hare and Meath (1987) differ considerably in the absolute values of cross sections. Discrepancies were observed in comparisons of cross sections of other fragment ions resulting from the ionization and dissociate ionization of NH3.

Rao, M. V. V. S.↗
NASA NTRS1974

Photolysis of CO-NH3 mixtures and the Martian atmosphere

It has already been noted (Ferris and Nicodem, 1972) that although neither CO2 nor H2O affected the rate of NH3 photolysis, CO accelerated the photodecomposition of ammonia, with the formation of a solid product. The photolysis of NH3 in the presence of CO is investigated in greater detail not only because of the potential significance to atmospheric photochemistry on Mars, but also because of the possibility of photocatalytic reactions of NH3 and CO on the Martian surface and in the interstellar medium. These photoreactions may also have occurred on the primitive earth.

Ferris, J. P.↗
NASA NTRS1976

Rotational excitation of symmetric top molecules by collisions with atoms: Close coupling, coupled states, and effective potential calculations for NH3-He

The formalism for describing rotational excitation in collisions between symmetric top rigid rotors and spherical atoms is presented both within the accurate quantum close coupling framework and also the coupled states approximation of McGuire and Kouri and the effective potential approximation of Rabitz. Calculations are reported for thermal energy NH3-He collisions, treating NH3 as a rigid rotor and employing a uniform electron gas (Gordon-Kim) approximation for the intermolecular potential. Coupled states are found to be in nearly quantitative agreement with close coupling results while the effective potential method is found to be at least qualitatively correct. Modifications necessary to treat the inversion motion in NH3 are discussed.

Green, S.↗
NASA NTRS1981

Irradiation of NH3-CH4 mixtures as a model of photochemical processes in the Jovian planets and Titan

The reactions occurring upon the ultraviolet irradiation of ammonia-methane mixtures are investigated in a simulation of the atmospheric chemistry of the Jovian planets and Titan. Gas mixtures were irradiated at 185 nm at temperatures from 156-298 K, and product and reactant concentrations were determined by means of gas chromatography. The ratio of the moles of CH4 lost per mole of NH3 decomposed is found to be 0.25, with the extent of CH4 decomposition independent of temperature. The absence of a temperature effect suggests that nonthermal atoms, probably hydrogen, initiate CH4 decomposition by the extraction of a hydrogen atom. A decrease in CH4 loss with increasing pressure or the addition of other gases to the photolysis mixture, and the lack of an increase in NH3 photolysis with CH4 pressure support this mechanism. Major reaction products obtained include C2H2, C3H8 or CH3NH2, and C4H10. Considerations of atmospheric concentrations of H2 and He indicate that NH3 photolysis does not contribute to CH4 decomposition on Jupiter, Saturn, Uranus, and Neptune, although it may have had a role in the formation of the Titan atmosphere.

Ferris, J. P.↗
NASA NTRS1982

Photochemistry of NH3, CH4 and PH3 - Possible applications to the Jovian planets

It is found that the photolysis of NH4 at 185 nm in the presence of a two-fold excess of CH4 results in the loss of about 0.25 mole of CH4 per mole of NH3 decomposed. The loss is shown to arise from the abstraction of hydrogen atoms from CH4 by photolytically generated hot hydrogen atoms. It is concluded that NH3 photolysis in the H2-abundant atmosphere of Jupiter is not responsible for the presence of the carbon compounds observed there, such as ethane, acetylene, and hydrogen cyanide, but may have had a role in the early atmosphere of Titan. Also, it is found that the photolysis of PH3 with a 206 nm light source gives P2H4, which in turn is converted to a red-brown solid. The course of the photolysis is not changed appreciably when the temperature is lowered to 157 K except that the concentration of P2H4 increases, while the presence of H2 has no effect on the P2H4 yield. Photolysis of 9:1 NH3:PH3 is found to give a rate of decomposition of PH3 that is comparable with that observed by the direct photolysis of PH3 and comparable amounts of the red-brown solid and P2H4 are observed. In addition, the implications of these results for the structures of the compounds responsible for the wide array of colors observed in the atmosphere of Jupiter are examined.

Ferris, J. P.↗
NASA NTRS1983

Photodissociation of NH3 at 106-200 nm

The absorption and fluorescence cross sections for NH3 are measured in the 106-200 nm region using synchrotron radiation as the light source. The threshold wavelengths for the production of the NH (b to X) and NH (c to a) emissions from NH3 dissociation are measured and compared with previous measurements. The heat of formation of NH determined from these thresholds agrees well with the value determined from thermochemical data. The process of dissociation of NH3 into NH2(2AL) and H2(S) has a significant quantum yield whose maximum at 134 nm is about twice the NH(c) production yield. All the vibronic levels of the B and C states produce the NH2(2A1) emission, contrary to previous theoretical interpretations.

Suto, M.↗
NASA NTRS1984

The composition of Saturn's atmosphere at northern temperate latitudes from Voyager IRIS spectra - NH3, PH3, C2H2, C2H6, CH3D, CH4, and the Saturnian D/H isotopic ratio

The vertical distributions and mixing ratios of minor constituents in the northern hemisphere of Saturn are investigated. Results are obtained for NH3, PH3, C2H2, C2H6, CH3D, and CH4; the D/H ratio is obtained from the CH4 and CH3D abundances. The NH3 mixing ratio in the upper atmosphere is found to be compatible with the saturated partial pressure. The inferred PH3/H2 ratio of 1.4 + or - 0.8 x 10 to the -6th is higher than the value derived from the solar P/H ratio. The stratospheric C2H2/H2 and C2H6/H2 ratios are, respectively, 2.1 + or - 1.4 x 10 to the -7th and 3.0 + or - 1.1 x 10 to the -6th; the latter decreases sharply below the 20-50 mbar level. The results for CH3D/H2 and CH4/H2 imply an enrichment of Saturn's upper atmosphere in carbon by a factor of at least three over the solar abundance. The interpretation of two NH3 lines in the five-micron window suggests a NH3/H2 ratio at the two bar level below the solar value.

Courtin, R.↗
NASA NTRS1990

Density dependence of the 5 micron infrared spectrum of NH3

Measurements of dilute mixtures of NH3 in H2 were made in the window region 1900-2100/cm of the NH3 spectrum to determine is behavior with increasing pressure of H2. The spectra of pure H2, pure NH3, and mixtures of the two, in the total pressure range from 2.38 to 8.17 atm at 309 K, were obtained with a 975-cm white-cell. Synthetic spectra were calculated using precise line strengths, line positions, and a Lorentz profile. The experimental and calculated spectra are in reasonably good agreement, except that the former is super-imposed on a rather flat background not given by the calculation. A possible mechanism for this background is suggested.

Chapados, Camille↗
NASA NTRS1992

The tropospheric abundances of NH3 and PH3 in Jupiter's Great Red Spot, from Voyager IRIS observations

The tropospheric abundances of NH3 and PH3 in Jupiter's Great Red Spot (GRS) are presently determined on the basis of a group of Voyager IRIS spectra, and compared with those of the surrounding South Tropical Zone (STZ) obtained from another two groups of IRIS spectra, in order to characterize the GRS's chemistry and dynamics. Although the GRS is believed to be a region of strong vertical transport, NH3 depletion is surprisingly found to occur below the tropopause within the GRS. Since one of the STZ's selections has a temperature-pressure profile similar to that of the GRS below the 300 mbar level, condensation cannot explain the low NH3 abundance in the GRS.

Griffith, Caitlin A.↗
NASA NTRS1995

Shock-excited NH3 (3, 3) masers in the NGC 6334 star-forming region

We report the discovery of four NH3 (3, 3) masers in the NGC 6334 star formation region. The masers are found in two of the seven far-infrared continuum sources where high-mass star formation is taking place in this molecular cloud. These masers occur at the ends of high-velocity molecular outflows; no maser emission was found near regions without high-velocity outflows. The NH3 masers are not associated with any other type of maser. These results confirm that the NH3 (3, 3) masers are caused by shocks and probably mark the location where the molecular outflow jet impinges upon the ambient medium.

Kraemer, Kathleen E.↗
NASA NTRS1995

NH3, H2S, and the Radio Brightness Temperature Spectra of the Giant Planets

Recent radio interferometer observations of Neptune enable comparisons of the radio brightness temperature (T(sub B)) spectra of all four giant planets. This comparison reveals evidence for fundamental differences in the compositions of Uranus' and Neptune's upper tropospheres, particularly in their ammonia (NH3) and hydrogen sulfide (H2S) mixing ratios, despite those planets' outward similarities. The tropospheric abundances of these constituents yield information about their deep abundances, and ultimately about the formation of the planets from the presolar nebula (Atreya et al.). Figures 1, 2, 3, and 4 show the T(sub B) spectra of Jupiter, Saturn, Uranus, and Neptune, respectively, from 0.1 to tens of cm wavelength. The data shown are collected from many observers. Data for Jupiter, Saturn, and Uranus are those cataloged by de Pater and Massie (1985), plus the Saturn Very Large Array (VLA) data by Grossman et al. Figure 3, Uranus, shows only data acquired since 1973. Before 1973 Uranus' T(sub B) increased steadily as its pole moved into view, causing significant scatter in those data. Neptune data at greater than 1 cm, all taken at the VLA, are collected from de Pater and Richmond, de Pater et al., and Hofstadter. For a variety of reasons, such as susceptibility to source confusion, single-dish data at those wavelengths are much noisier than the more reliable VLA data and have been ignored. Single-dish data by Griffin and Orton shortward of 0.4 cm are shown, along with the Owens Valley Radio Observatory (interferometer) datum at 0.266 cm by Muhleman and Berge. Spectra of Jupiter, Saturn, and Neptune share certain gross characteristics. In each spectrum, T(sub B) at 1.3 cm is approximately 120-140 K, less than approximately 30 K different from that at 0.1 cm. All three spectra show a break in slope at or near 1.3 cm, with T(sub B) increasing fairly rapidly with wavelength longward of 1.3 cm. Visible and IR spectroscopy show that NH3, whose strong inversion spectrum peaks at appropximately 1.3 cm, is an important tropospheric species at Jupiter and Saturn. Its signature on the Jovian radio spectrum is obvious, causing the prominent "hole" at 1.3 cm. At Saturn it is more subdued but is the source of that spectrum's change in slope at 1.3 cm. Radiative transfer models of Jupiter and Saturn with near-solar deep NH3 abundances agree well with the data (e.g., de Pater).

Spilker, Thomas R.↗
NASA NTRS2013

Photo-Induced Deuterium Enrichment in Residues Produced from the UV Irradiation of Pyrimidine in H2O and H2O+NH3 Ices

Organic compounds found in meteorites often show isotopic signatures of their interstellar/protosolar heritage as enrichments in D and 15N. Meteoritic organics found to be enriched in D include amino acids, hydroxy and dicarboxylic acids, as well as polycyclic aromatic hydrocarbons (PAHs). Processes that can produce isotopic enrichments in presolar/protosolar materials include gas-phase ion-molecule reactions, gas-grain surface reactions, and unimolecular photo-dissociation reactions involving PAHs. Because many molecules in interstellar clouds are enriched in D, the presence of D anomalies in meteorites is thought to originate from preserved or slightly altered interstellar/protostellar materials. However, the link between isotopic enrichments seen in space and those in meteoritic compounds and their relationship remain unclear. In this work, we present results of hydrogen isotopic fractionation for compounds in organic residues produced from the UV irradiation using an H2- discharge UV lamp of H2O:pyrimidine = 20:1 and H2O:NH3:pyrimidine = 20:2:1 ice mixtures at low temperature (is less than 20 K). After irradiation, the resulting residues are dissolved in H2O and analyzed with gas chromatography-mass spectrometry coupled with isotope ratio mass spectrometry (GC-MS/IRMS) [1], following a protocol similar to that used for previous analyses of comparable samples [2,3]. We used this technique to measure compound-specific D/H isotopic ratios for the initial pyrimidine and for two photo-products present in the residues, namely, 2,2'-bipyrimidine and an unidentified bipyrimidine isomer [2-4]. Measuring D enrichments in bipyrimidines has the advantage that the H atoms on these molecules are not easily exchangeable with other compounds, in particular the H2O and NH3 present in the ices or the solvents used to extract the samples for GC-MS/IRMS measurements. The δD value for the initial pyrimidine, measured with a high-temperature conversion elemental analyzer connected to the IRMS, was found to be -30% per mille. Preliminary measurements made on a residue produced from the UV irradiation of an H2O:NH3:pyrimidine = 20:2:1 ice mixture indicate δD values of +118% per mille for 2,2'- bipyrimidine and +92% per mille for the other bipyrimidine isomer, and therefore show a significant D enrichment during the photo-processing and warm-up that lead to their formation [5]. New measurements are currently being performed on a number of residues produced from simpler H2O:pyrimidine = 20:1 ice mixtures under different experimental conditions and will be presented here.

Laboratory Astrochemistry↗
NASA NTRS1975

A laboratory Atlas of the 5 nu-1 NH3 absorption band at 6475 A with applications to Jupiter and Saturn

A complete atlas of the 5 nu-1 absorption band of NH3 is presented together with measurements of the total band intensity, line intensities, and self-broadening coefficients. The spectrum, which is displayed in the interval from 6418 to 6550 A, was obtained photoelectrically at a pressure of 0.061 atm, and many more lines were seen in this spectrum than in a previous one obtained at a pressure of 0.39 atm. The band intensity is used to derive the NH3 abundance in the atmospheres of Jupiter and Saturn, and the abundances in a single vertical path are found to be about 10 m amagat for Jupiter and 2 m amagat for Saturn. These results are shown to be in agreement with previous results obtained from higher resolution photographic spectra.

Giver, L. P.↗
NASA NTRS1975

Ultraviolet-gas phase and -photocatalytic synthesis from CO and NH3

Ammonium cyanate is identified as the major product of the photolysis of gaseous NH3-CO mixtures at 206.2 or 184.9 nm. Lesser amounts of urea, biurea, biuret semicarbazide, formamide and cyanide are observed. A series of 18 reactions underlying the formation of photolysis products is presented and discussed. Photocatalytic syntheses of C-14-urea, -formamide, and -formaldehyde are carried out through irradiation of (C-14)O and NH3 in the presence of Vycor, silica gel, or volcanic ash shale surfaces. The possible contributions of the relevant reactions to the abiotic synthesis of organic nitrogen compounds on Mars, the primitive earth, and in interstellar space are examined.

Hubbard, J. S.↗
NASA NTRS1978

NH3 in IRC plus 10216

Ammonia was detected in the circumstellar envelope of IRC +10216 by means of three infrared absorption lines in the nu sup 2 band around 950/cm. The lines are fully resolved at a resolution of 0.22 km/sec and indicate that most of the circumstellar gas is accelerated to expansion velocities around 14 km/sec within a few stellar radii. The NH3 profiles indicate a rotational temperature between 400 and 700 K, and H2 density between 10 to the 8th power/cu cm and 10 to the 10th power/cu cm, and NH3 column density of 10 to the 17th power/sq cm. The H2 density indicates that the mass of the circumstellar envelope within a 1 arcsec radius is approximately 0.1 solar masses.

Betz, A. L.↗
NASA NTRS1980

Energy transfer in NH3-He collisions

The paper presents a new electron gas intermolecular NH3-He potential determined by the Hartree-Fock results of Davis, Boggs, and Mehrotra (1979) with semiempirical long-range induction and dispersion terms. The resulting potential agrees with beam scattering and pressure broadening measurements; it was also found that the quadrupole induced dipole interaction is not as effective as the short range anisotropy. It was concluded that discrepancies remain in the quantitative description of energy transfer in the NH3-He system; discrepancies result from improper consideration of the dependence of cross-sections on degenerate magnetic quantum levels in the experimental investigation.

Green, S.↗
NASA NTRS1982

The tropospheric gas composition of Jupiter's north equatorial belt (NH3, PH3, CH3D, GeH4, H2O) and the Jovian D/H isotropic ratio

The gas composition of the troposphere of Jupiter in the clearest regions of the North Equatorial Belt (NEB) was derived from the Voyager 1 IRIS data. The infrared spectrum for this homogeneous cloud free region was modeled to infer altitude profiles for NH3, PH3, GeH4 and H2O. The Profiles for NH3 and PH3 were found to be depleted in the upper troposphere but otherwise in agreement with their solar values at the 1 bar level. The mole fraction for CH3D was determined to be 3.5(+1.0 or -1.3) x 10 to the minus 7th power. The GeH4 mole fraction of 7+ or -2 x 10 to the minus 10th power at the 2 to 3 bar level is a factor of 10 lower than the solar value. The H2O mole fraction is approximately 1 x 0.00001 at the 2.5 bar level and is increasing to approximately 3 x 0.00001 at 4 bars where it is a factor of 30 lower than solar. Using IRIS infrared values for the mole fractions of CH3D and CH4 a value of D/H = 3.6(+1.0 or -1.4)x 0.00001 is derived. Assuming this Jovian D/H ratio is representative of the protosolar nebula, and correcting for chemical galactic evolution, yields a value of 5.5 - 9.0 x 0.00001 for the primordial D/H ratio and an upper limit of 1.8 to 2.4 x 10 to the minus 31st power cu cm for the present day baryon density.

Kunde, V.↗
NASA NTRS1983

The ground state far infrared spectrum of NH3

The NH3 far infrared spectrum is particularly useful for the study of planetary composition and atmospheric dynamics. Studies of this spectrum were conducted by Dowling (1969), Helminger et al. (1971), and Urban et al. (1981). Sattler et al. (1981) have reported measurements of a few nu2 lines with tunable diode lasers. By using simple sum rules, these lines and accurate ground state inversion lines considered by Poynter and Kakar (1975) have been employed in the present investigation to deduce a few of the far infrared ground state transitions. An extensive set of high signal/noise, high resolution (0.0048 per cm) scans of the nu2 bands of NH3 from about 600 per cm through about 1300 per cm ait a series of low pressures have been made in order to accurately determine both the line positions and strengths. The obtained data provide line positions with an absolute accuracy of about 0.0001 per cm in the more favorable cases.

Poynter, R. L.↗