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Transition probabilities for the second negative band system of O2(+) are computed using the dipole transition moment presented by Wetmore et al. (1984). Vibrational levels v double prime = 0 - 54 of the X2Pi(g) ground state and v prime = - 33 of the excited A2Pi(u) state are included. Franck-Condon factors for ionization-excitation of O2 to O2(+) are also presented.
Data from the visible-airglow experiment on the Atmosphere Explorer-E satellite have been used to determine the quantum yields of O (1S) and O (1D) from the dissociative recombination of O2(+) based on a constant total recombination rate from each vibrational level. A range of values between 0.05 and 0.18 has been obtained for the quantum yield of O (1S) and shows a positive correlation with the extent of the vibrational excitation of O2(+). The quantum yield of O (1D) has been measured to be 0.9 + or - 0.2, with no apparent dependence on the vibrational distribution of O2(+).
Experiments were conducted to determine whether dissociative adsorption is a possible limitation of the oxygen permeability through Ag, using the upstream glow-discharge dissociation of O2 and CO2 to provide a gas phase source of atomic oxygen. Results suggest that the dissociative adsorption step limits the supply of oxygen atoms to the upstream side of the membrane. When the upstream O2 was replaced by an equal pressure of CO2 in absence of glow discharge, only a small permeation signal was observed; the application of the glow discharge increasded the oxygen transport flux from 3.25 x 10 to the 12th/sq cm per sec to 1.74 x 10 to the 14th/sq cm per sec. It is suggested that this method of separating O2 from a CO2-rich atmosphere may be considered for providing oxygen for the astronauts in a manned expedition to Mars.
The hot hydrogen atom reaction, H + O2 yields OH + O, has been studied at a center of mass collision energy of 1.6 eV. H atoms were generated by 266 nm photolysis of HI in a mixture of HI and O2 at 293 K. The OH product was probed by laser induced fluorescence and the nascent OH vibrational, rotational, and fine structure distributions were determined. The OH(v=0)/OH(v=1) vibrational branching ratio was measured to be 1.72 + or - 0.09. The data suggest that the H + O2 reaction at this collision energy proceeds via two competing mechanisms: reaction involving a long-lived complex and direct reaction.
It is demonstrated that a complete-active-space self-consistent-field (CASSCF) (2p)/MRCI + Q (multireference configuration interaction with a Davidson correction) description in a (13s8p6d 4f2g)/((5s4p3d 2f1g) atomic natural orbits (ANO) basis set supplemented with diffuse functions provides a quantitative description of the six lowest states of O2. The calculated potentials are within 0.05 eV (1.2 kilocal/mol) of accurate experimental results. The importance of substantially expanding the primitive basis set has been investigated, and it is demonstrated that such expansions yield insignificant improvement in the spectroscopic constants. Potential energy curves have also been reported for the weakly bound states of O2. The 5Pi(g) state is estimated to have a D(e) of 0.16 +/- 0.03 eV. The upper bound of D(e) is found to be sufficiently large that the importance of this state as a precursor for the formation of O2 (b 1Sigma(t)(+)) and O(1S) should be reconsidered.
O2 cross sections from 49,000 to 57,000/cm have been fitted with temperature dependent polynomial expressions, providing an accurate and efficient means of determining Schumann-Runge band cross sections for temperatures between 130 and 500 K. The least squares fits were carried out on a 0.5/cm spectral grid, using cross sections obtained from a Schumann-Runge line-by-line model that incorporates the most recent spectroscopic data. The O2 cross sections do not include the underlying Herzberg continuum, but they do contain contributions from the temperature dependent Schumann-Runge continuum. The cross sections are suitable for use in UV transmission calculations at high spectral resolution. They should also prove useful for updating existing parameterizations of ultraviolet transmission and O2 photolysis.
Technique for generating supply of highly pure O2 from CO2 developed. First, atomic oxygen at useful partial pressure generated by glow-discharge dissociation of CO2. Atomic oxygen formed in vicinity of hot silver membrane and permeates through membrane to downstream region, where thermally recombined into O2 and pumped away to storage tank. Pure oxygen stored suitable for human consumption and other uses. Originally developed to convert Martian atmosphere of CO2 to O2 for astronaut consumption. Other potential applications include purification of atmospheres in Space Shuttle and Space Station Freedom. Byproduct CO must be handled by other techniques.
Using a crossed electron beam-molecular beam collision geometry and the relative flow technique measurements have been made to generate a uniform set of electron impact ionization cross-section data for O2 for electron impact energies from threshold to 1000 eV. Present values of total, partial and dissociative ionization cross-sections are compared with previously published data. Cross-sections for the formation of O2(+) from O2 have been measured for the first time.
Parameters are estimated for a hypothetical, well stirred, continuous-feed electrolytic cell that converts 20 percent of a lunar soil feedstock to O2 gas, 26 percent to Fe-Si metal, 13 percent to spinel, and 41 percent to slag. Advantages of a molten Fe-Si cathode for trapping metal on reduction, a relatively conductive steady-state composition in equilibrium with spinel (a proposed container material), and close electrodes (less than 1 cm cathode-anode distance) are discussed. To produce 1 ton of O2, about 6 MHW of energy are required for the electrolysis and IR heating within the melt, and another about 6 MHW may be introduced as waste heat through internal resistance of the electrodes. Thus, to produce 1 ton of O2 per 24 hours, about 0.5 MW of power delivered to the cell would be required.
An accurate line-by-line model is used to evaluate effects of absorption in the Schumann-Runge bands of O2 on transmission of UV radiation. The model is used to evaluate rates of photolysis for N2O, CFCl3, and CF2Cl2, and to infer global loss rates and instantaneous lifetimes appropriate for 1980. A parameterized version of the line-by-line model enabling rapid evaluation of transmission in the Schumann-Runge region is described. Photochemical calculations employing the parameterization and constrained by data from the Atmospheric Trace Molecule Spectroscopy experiment are used to examine the budget of odd oxygen. Consistent with previous studies, it is shown that photochemical loss of odd oxygen exceeds production by photolysis of O2 for altitudes above 40 km. The imbalance between production and loss is shown to be consistent with a source of odd oxygen proportional to the product of the mixing ratio and photolysis rate of ozone, which suggests that processes involving vibrationally excited O2 may play an important role in production of odd oxygen.
The wave-driven fluctuations in the O2(0-1) atmospheric nightglow is modeled and the parameter (eta) is calculated using a model that accounts for either three-body recombination of atomic oxygen atoms alone to form the O2(b exp 1 Sigma(g)(+)) state directly, or by the further inclusion of the process that allows the formation of the O2(c exp 1 Sigma(u)(-)) intermediate state. The calculations are performed for a latitude of 18 deg N and for the months of March and June. The general results, which display how (eta) varies with wave period, horizontal wavelength, season, and chemical scheme, show that for given values of wave period and horizontal wavelength it is not possible to discriminate between seasonal effects and between the effects of different chemical schemes at evanescent and short gravity wave periods. It is shown that, when quenching by atomic oxygen is ignored, the resulting values of (eta) calculated with the complete chemistry are similar to those obtained from the three-body recombination scheme alone.
We have compared three photochemical diurnal models of O3 and OH in the upper stratosphere and mesosphere which use different techniques for calculating the absorption of solar ultraviolet radiation by the O2 Schumann-Runge bands. One model uses a detailed line-by-line representation of the O2 cross section from 1750-2050 A, while the two others use lower resolution, parameterized cross sections. Using the parameterized cross sections, the calculated O3 profiles for both day and night agree with those obtained from the line-by-line model to within 6%. This appears to eliminate inaccuracies in the parameterized O2 cross section as a major cause of previously reported model O3 deficits. A portion of the residual differences from the line-by-line model are attributed to inaccuracies in the calculated H2O photolysis rate. A parameterized H2O cross section is offered which improves the accuracy of this calculation.
Samples of HgBa2CuO(4+delta) (Hg-1201) were annealed under various conditions. After carefully controlling annealing time, annealing temperature (T(sub a)) and O2 partial pressure (P(sub 0)), we were able to find the reversible annealing conditions for Hg-1201. Under 1 atm O2 at 260 C less than or equal to T(sub a) less than or equal to 400 C, the obtained T(sub c) is nearly the same (approximately 97 K). However, it decreases quickly with T(sub a) greater than 300 C in high vacuum (P(sub 0) approximately 10(exp -8) atm), and reaches zero at T(sub a) = 400 C. On the other hand, T(sub c) decreases with the decrease of T(sub a) in high-pressure O2 (approximately 500 atm) and reaches approximately 20 K at about 240 C. In the entire annealing region, the oxygen surplus varies significantly from 0.03 to 0.4, and a wide range of T(sub c) variation (0 goes to 97 K goes to 20 K) was obtained with anion doping alone.
Laser flash photolysis of Cl2/O2 mixtures has been employed in conjunction with Cl((sup 2)P(sub 3/2)) detection by time-resolved fluorescence spectroscopy to investigate equilibration kinetics for the reactions Cl + O2 + O is in equilibrium with ClOO + O2 at temperatures of 181-200 K and O2 pressures of 15-40 Torr. The third-order rate coefficient for the association reaction at 186.5 +/- 5.5 K is (8.9 +/- 2.9) x 10(exp -33) cm(exp 6) molecule(exp -2) s(exp -1) and the equilibrium constant (K(p)) at 185.4 K is 18.9 atm(exp -1) (factor of 1.7 uncertainty). A third law analysis of our data leads to a value for the Cl-OO bond dissociation energy of 4.76 +/- 0.49 kcal mol(exp -1).
The infrared spectra of CO frozen in non-polar ices containing N2, CO2, O2, and H2O, and the ultraviolet photochemistry of these interstellar/precometary ice analogs are reported. The spectra are used to test the hypothesis that the narrow 2140/cm (4.673 micrometer) interstellar absorption feature attributed to solid CO might be produced by CO frozen in ices containing non-polar species such as N2 and O2. It is shown that mixed molecular ices containing CO, N2, O2, and CO2 provide a very good match to the interstellar band at all temperatures between 12 and 30 K both before and after photolysis. The optical constants (real and imaginary parts of the index of refraction) in the region of the solid CO feature are reported for several of these ices.
This study was designed to investigate the role of tissue oxygenation in some of the factors that are thought to regulate muscle respiration and metabolism. Tissue oxygenation was altered by reductions in O2 delivery (muscle blood flow x arterial O2 content), induced by decreases in arterial PO2 (PaO2). O2 uptake (VO2) was measured in isolated in situ canine gastrocnemius at rest and while working at two stimulation intensities (isometric tetanic contractions at 0.5 and 1 contractions/s) on three separate occasions, with only the level of PaO2 (78, 30, and 21 Torr) being different for each occasion. Muscle blood flow was held constant (pump perfusion) at each work intensity for the three different levels of PaO2. Muscle biopsies were obtained at the end of each rest and work period. Muscle VO2 was significantly less (P less than 0.05) at both stimulation intensities for the hypoxemic conditions, whereas [ATP] was reduced only during the highest work intensity during both hypoxemic conditions (31% reduction at 21 Torr PaO2 and 17% at 30 Torr). For each level of PaO2, the relationships between the changes that occurred in VO2 and levels of phosphocreatine, ADP, and ATP/ADP.P(i) as the stimulation intensity was increased were significantly correlated; however, the slopes and intercepts of these lines were significantly different for each PaO2. Thus a greater change in any of the proposed regulators of tissue respiration (e.g., phosphocreatine, ADP) was required to achieve a given VO2 as PaO2 was decreased.(ABSTRACT TRUNCATED AT 250 WORDS).
Simulations using the HITRAN database and other data have been carried out to select the optimum laser wavelengths for the measurements of CO2 and O2 concentrations with the application to the ASCENDS mission. The accuracy set forth for the ASCENDS mission requires accurate line-by-line calculations involving the use of non-Voigt line shapes. To aid in achieving this goal, improved CO2 and O2 transmission calculation methods are being developed. In particular, line-by-line transmission modeling of CO2 was improved by implementing non-Voigt spectral lineshapes. Ongoing work involves extending this approach to the O2 molecule 1.26-1.27micron spectral band.
The Active Sensing of CO2 Emissions over Nights Days and Seasons (ASCENDS) mission recommended by the NRC Decadal Survey has a desired accuracy of 0.3% in carbon dioxide mixing ratio (XCO2) retrievals requiring careful selection and optimization of the instrument parameters. NASA Langley Research Center (LaRC) is investigating 1.57 micron carbon dioxide as well as the 1.26-1.27 micron oxygen bands for our proposed ASCENDS mission requirements investigation. Simulation studies are underway for these bands to select optimum instrument parameters. The simulations are based on a multi-wavelength lidar modeling framework being developed at NASA LaRC to predict the performance of CO2 and O2 sensing from space and airborne platforms. The modeling framework consists of a lidar simulation module and a line-by-line calculation component with interchangeable lineshape routines to test the performance of alternative lineshape models in the simulations. As an option the line-by-line radiative transfer model (LBLRTM) program may also be used for line-by-line calculations. The modeling framework is being used to perform error analysis, establish optimum measurement wavelengths as well as to identify the best lineshape models to be used in CO2 and O2 retrievals. Several additional programs for HITRAN database management and related simulations are planned to be included in the framework. The description of the modeling framework with selected results of the simulation studies for CO2 and O2 sensing is presented in this paper.