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Photoelectron angular distributions for Ar, Xe, N2, O2, CO, CO2, and NH3 were obtained at 584 A by observing the photoelectrons at a fixed angle and simply rotating the plane of polarization of a highly polarized photon source. The radiation from a helium dc glow discharge source was polarized (84%) using a reflection type polarizer.
The significance of gas phase reactions in determining the nuclear structure of comets is discussed. The sublimation of parent molecules such as H2O, CH4, CO2, and NH3 from the surface of the nucleus and their subsequent photodissociation and ionization in forming observed cometary molecular species are elaborated.
The eddy diffusion coefficient is estimated as a function of altitude, separately for the Jovian troposphere and mesosphere. Complex organic molecules produced by the Ly alpha photolysis of methane may possibly be the absorbers in the lower mesosphere which account for the low reflectivity of Jupiter in the near ultraviolet. The optical frequency chromophores are localized at or just below the Jovian tropopause. Candidate chromophore molecules must satisfy the condition that they are produced sufficiently rapidly that convective pyrolysis maintains the observed chromophore optical depth. The condition is satisfied if complex organic chromophores are produced with high quantum yield by NH3 photolysis at less than 2,300 A. Jovian photoautotrophs in the upper troposphere satisfy this condition well, even with fast circulation, assuming only biochemical properties of comparable terrestrial organisms. An organism in the form of a thin, gas filled balloon can grow fast enough to replicate if (1) it can survive at the low mesospheric temperatures, or if (2) photosynthesis occurs in the troposphere.
Ammonia (NH3) was photolyzed at 213.9 nm in the presence of NO2 at 25 C in order to study the reactions of NH2 with NO2. The products included NO, with a quantum yield of 1.0. The other measured products of the reaction were N2 and N2O with respective quantum yields of 0.94 plus or minus 0.10 and 0.3 in the presence of small amounts of He and 0.65 plus or minus 0.15 and 0.13 in the presence of a large excess of He. The quantum yield for NO2 consumption was 6.0 plus or minus 2.0 in the absence of He. These results are explained in terms of various reactions.
A description is given of calculations which demonstrate that metallic ammonium, at least in the form envisaged by Ramsey (1951), is unstable at all pressures. On the basis of the computational results it is concluded that monovalent metallic ammonium is never the thermodynamically favored phase for an NH3-1/2H2 mixture.
Temperature profiles for low latitude regions of Jupiter in the 1.0-0.1 bar pressure regime are recovered from Pioneer 10 infrared radiometer data. The temperature near 0.1 bar is 108-117 K, depending on the overlying thermal structure assumed. For the South Equatorial Belt (SEB), the temperature at 1.0 bar is 170 K, assuming an adiabatic lapse rate in the deep atmosphere. The South Tropical Zone temperature at this level is 155 K if pure gaseous absorption is assumed. The temperature is much closer to that in the SEB, assuming the presence of an optically opaque cloud near the 0.6 atm (145 K) level. Such a cloud presence in the STrZ may be correlated with the visible and 5 micron appearance of the planet and with NH3 saturation just below this position. The molar fraction of H2 most consistent with the data is 0.91 + or - 0.08. The effective temperatures of the SEB and STrZ are 127.6 and 124.2 K, respectively. A discrepancy with the preliminary neutral atmosphere inversion of Pioneer 10 radio occultation data remains unexplained.
Absolute rate constants for the deactivation of O(1D) atoms by some atmospheric gases have been determined by observing the time-resolved emission of O(1D) at 630 nm. O(1D) atoms were produced by the dissociation of ozone via repetitive laser pulses at 266 nm. Absolute rate constants for the relaxation of O(1D) at 298 K are reported for N2, O2, CO2, O3, H2, D2, CH4, HCl, NH3, H2O, N2O, and Ne. The results obtained are compared with previous relative and absolute measurements reported in the literature.
Remote sensing of the concentration and vertical distribution of atmospheric gases using an infrared heterodyne spectrometer (IHS) has been investigated, and a dual (C-13)(O-16)2 laser multichannel IHS has been developed. Analyses of nadir thermal-radiance measurements from an aircraft at 10-km altitude and of solar absorption measurements from the ground indicate that initial applications of the IHS to tropospheric measurements of NH3 and O3 are feasible with measurement precisions ranging from 0.5 to 2 ppb and 20 to 30 ppb, respectively. These analyses have included effects of potential retrieval-error sources and have resulted in specifications of measurement modes, optimum signature lines, required system parameters, and expected sensitivities. Preliminary instrument performance data are presented.
Atmospheric infrared emission and absorption spectra obtained from aircraft and balloon-borne spectrometers are presented. From such spectra, mixing ratio vs altitude profiles are derived for several minor constituents. Recent results for HNO3, CF2Cl2, CFCl3, and HF are presented. In addition, the feasibility of infrared detection of other trace constituents, such as HCl, HF, NH3, NO and SO2, against the rest of the atmospheric background is studied. From this study, made on a line-by-line basis for 'state of the art' airborne spectrometers, potential spectral features for detection of the trace constituents are isolated.
A spectrum of Io from 0.86 to 2.7 microns with a resolution of 3.36 per cm and a signal to rms noise ratio of 120 is presented. No absorptions due to any atmospheric constituents on Io could be found in the spectrum. Upper limits of 0.12 cm-atm for NH3, 0.12 cm-atm for CH4, 0.4 cm-atm for N2O, and 24 cm-atm for H2S were determined. Laboratory spectra of ammonia frosts as a function of temperature were compared with the spectrum of Io and showed this frost not to be present at the surface of Io. A search for possible resonance lines of carbon, silicon, and sulfur, as well as the 1.08-micron line of helium, proved negative. Upper emission limits of 60, 18, 27, and 60 kilorayleighs, respectively, were established for these lines.
A series of models of Uranus is computed assuming that Uranus consists of a core of rocky material surrounded by a convecting envelope rich in H2O, NH3, and CH4. It is found that good fits are obtained to the observed parameters when the CH4:H2 ratio is of the order of 0.1. It is suggested that the rotational period of Uranus is roughly 18 h.
The visible (0.3 to 1.03 microns) spectral reflectances of N2O, NH3, H2S, and NH4HS frosts and mixtures of these frosts as well as their UV-irradiated products have been measured. These spectra are compared with the spectra of the Galilean satellites of Jupiter, Saturn's rings, and Saturn's satellites to place limits on their surface compositions.
Spectrophotometric observations from 2 to 4 microns and from 8 to 13 microns of several infrared sources associated with molecular clouds are reported. Narrow absorption features at 3.08 microns, attributed to interstellar ices, appear in all sources with a molecular cloud in the intervening line of sight. All sources showing ice absorptions also show broad absorption features, attributed to cold silicates, from 8 to 13 microns. The observed ice absorption profiles are all quite similar; however, they do not fit in detail Mie theory predictions of extinction for pure H2O or NH3 ices. The ratio of ice-to-silicate optical depths is found to vary, with most sources showing a ratio in the range 0.1-0.4. The ratio of visual extinction to ice absorption is found to increase rapidly from inside to outside the molecular cloud in NGC 2024.
Performance tests on an electro-optical model of an infrared sensor for remote measurements of trace atmospheric gases are detailed; the instrument utilized a sample of the gas to be measured as spectral filter. Also reported is the development of radiometric calibration equipment that determines responses to simulated pollution effects. Results show excellent agreement with theoretical performance predictions with the exception of nonuniform radiance responses. Balance stability to an accuracy better than the rms noise level was demonstrated for the EOM in both the NH3 and CO modes for a period of two days under laboratory conditions. Flight test results show that the temperature range of the absorption cell is restricted to 255 K or higher.
Nitrous oxide, methane, ammonia, and a number of other trace constituents of the earth's atmosphere have infrared absorption bands in the spectral range from 7 to 14 microns. Despite their small amounts, these gases can have a significant effect on the thermal structure of the atmosphere by transmitting most of the thermal radiation from the earth's surface to the lower atmosphere. In the present paper, this greenhouse effect is computed for a number of trace gases. The nature and climatic implications of possible changes in the concentrations of N2O, CH4, NH3, and HNO3 are discussed.
The spectrum of the 2-micron point source at the galactic center is presented over the range from 1.4 to 2.7 microns. The two-level-transition CO band heads are seen near 2.3 microns, confirming that the radiation from this source is due to a cool supergiant star. The heliocentric radial velocity is found to be - 173 (+ or -90) km/s and is consistent with the star being in orbit about a dense galactic nucleus. No evidence is found for Brackett-gamma emission, and no interstellar absorption features are seen. Upper limits for the column densities of interstellar H2, CH4, CO, and NH3 are derived.
Product distributions and rate constants for the reaction of ground state C(+) ions with O2, NO, HCl, CO2, H2S, H2O, HCN, NH3, CH4, H2CO, CH3OH, and CH3NH2 have been measured. Rate constants were obtained using ion cyclotron resonance trapped ion methods, and product distributions were obtained using a tandem mass spectrometer. Rapid carbon isotope exchange has also been observed in C(+)-CO collisions.
The paper examines the recombination of electrons with ammonium-series cluster ions, NH4(+)-(NH3)n, for two reasons: (1) NH4(+) may be a significant ion in the lower atmospheres of the earth and the outer planets, and (2) to investigate the weak temperature dependence of the cluster ion's recombination coefficient. A microwave afterglow mass spectrometer was used to determine the recombination coefficients for the first five members of the ammonium series, (18+) through (86+), at temperatures between 200 and 410 K. The electron temperature dependence of the recombination coefficient was determined for (35+) and (52+), the n = 1 and 2 cluster ions, over the temperature range 300-3000 K.