Engineering topics
Publications and source records attributed to Slanger, T. G..
A summary of our recent work using terrestrial nightglow spectra, obtained from astronomical instrumentation, to directly measure, or evaluate theoretical values for fundamental parameters of astrophysically important atomic lines.
Astronomical sky spectra, which are byproducts of long-slit observations with echelle spectrographs on large telescopes, provide a unique platform for studying the optical emissions of excited molecules and atoms in the terrestrial atmosphere that can greatly extend present knowledge based on laboratory spectra. This paper summarizes some of the advances that have been made in our understanding of the lower electronic states of O2 and other species from the sky spectra and from direct observations of the Venus nightglow.
Photolysis of vibrationally excited oxygen produced by ultraviolet photolysis of ozone in the upper stratosphere is incorporated into the Lawrence Livermore National Laboratory two-dimensional zonally averaged chemical-radiative-transport model of the troposphere and stratosphere. The importance of this potential contributor of odd oxygen to the concentration of ozone is evaluated based on recent information on vibrational distributions of excited oxygen and on preliminary studies of energy transfer from the excited oxygen. When energy transfer rate constants similar to those of Toumi et al. (1991) are assumed, increases in model ozone concentrations of up to 4.0% in the upper stratosphere are found, and the model ozone concentrations are found to agree slightly better with measurements, including recent data from the Upper Atmosphere Research Satellite. However, the ozone increase is only 0.3% when the larger energy transfer rate constants indicated by recent experimental work are applied to the model. An ozone increase of 1% at 50 km requires energy transfer rate constants one-twentieth those of the preliminary observations. As a result, vibrationally excited oxygen processes probably do not contribute enough ozone to be significant in models of the upper stratosphere.
Results are presented of measurements of the rotational and fine-structure level-specific linewidths in v = 0 and v = 2 of the O2 B3Sigma-sub-u(-) state, which were carried out using laser-induced fluorescence techniques applied to Schumann-Runge absorption transitions from vibrationally excited O2 X3Sigma-sub-g(-) system. These linewidths represent the first measurements reflecting relative predissociation rates among the B-state levels. The linewidths were found to vary considerably among the various energy levels.
In order to test the proposal that photodissociation of highly vibrationally excited O2 in the Schumann-Runge (SR) band is a source of upper stratospheric ozone, cross sections for the band and continuum absorption are calculated. Calculated maximum SR cross sections are in the 1-2 x 10 to the -18th sq cm range, with the O2(B) state contributing 2-3 orders of magnitude greater absorption than the 1 3Pi(u) state. For v-double prime = 12, it is shown that the SR band and continuum cross sections merge smoothly at 250 nm. It is shown that numerous processes, the most important of which is nonlinear photoabsorption, ultimately lead to the prediction that narrow laser line absorption in the 248-nm region should generate comparable O atom yields whether absorption is into the bands or the continuum. In the atmosphere, SR band absorption is the dominant process.
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Although 248-nm radiation falls 0.12 eV short of the energy needed to dissociate O2, large densities of ozone (O3) can be produced from unfocused 248-nm KrF excimer laser irradiation of pure O2. As soon as any O3 is present, it strongly absorbs the 248-nanometer radiation and dissociates to vibrationally excited ground state O2 (among other products), with a quantum yield of 0.1 to 0.15. During the laser pulse, a portion of these molecules absorb a photon and dissociate, which results in the production of three oxygen atoms for one O3 molecule destroyed. Recombination then converts these atoms to O3, and thus O3 production in the system is autocatalytic. A deficiency exists in current models of O3 photochemistry in the upper stratosphere and mesosphere, in that more O3 is found than can be explained. A detailed analysis of the system as it applies to the upper atmosphere is not yet possible, but with reasonable assumptions about O2 vibrational distributions resulting from O3 photodissociation and about relaxation rates of vibrationally excited O2, a case can be made for the importance of including this mechanism in the models.
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With the aid of new calculations on the transition moments between the six lowest states of O2 (Klotz and Peyerimhoff, 1986), absorption cross sections have been calculated for several oxygen continua. Reasonable agreement is achieved with recent experimental results, the comparison indicating an overestimation of the theoretical transition moment for the A-X system of 20-25 percent. With this adjustment, the calculated radiative lifetime for the O2(A) state is 150 ms, in close agreement with the currently used value. The continua cross sections indicate that absorption by O2(a) cannot be a significant atmospheric process.
An analysis has been made of the primary atomic and molecular products arising from O3 photodissociation at 1576 A. The yield of oxygen atoms is 1.90 + or - 0.30, of which 71 percent are O(3P) and 29 percent are O(1D). Since a primary yield greater than unity can only be a consequence of three-fragment dissociation, these results suggest that fragmentation into three O(3P) atoms, and production of O(1D) plus a singlet oxygen molecule, have comparable yields. Observation of prompt emission in the 7300-8100 A spectral region indicates that the singlet O2 is O2(b 1Sigma + g). Vibrational levels in the range v = 0-6 have been detected, the distribution corresponding to a vibrational temperature of 1000 K.
The photodissociation of O3 was investigated as a possible sources of N2O production in the stratosphere. Photolysis was conducted at 1576 A to generate the excited O2 states that react with N2 to form N2O. At this wavelength, there is a quantum yield of two for prompt production of oygen atoms, which is a consequence of the existence of two photodissociative channels giving comparable yields. One of these channels gives O(D1) and O2(b1sigma(+)subg), with a quantum yield of 0.6, whereas the other results in fragmentation of the O3, with production of three ground state oxygen atoms. The O2(b) is generated with vibrational excitation, and there are comparable populations in levels O to 3. These observations are the first to show O2(b) production from any photodissociative process, and were made under conditions in which the kinetics of vibrationally excited O2(b) can be studied. It appears that O3 photodissociation at 1576 A is not a good system for generating the higher electronic states of O2; it is likely that better results will be obtained at 1930 A.
The paper discusses the O(1S) yield from O3 photodissociation measured in the 1700-2400 A region using synchrotron radiation as a light source. An upper limit for the yield set at 0.1% for the entire photon energy range indicates that the contribution of O(1S) to atmospheric OH production is not significant. The spin restriction for going into the O(1S) + O2/X3Sigma(-)(g)/ channel appears to be the determining factor in the low yield. There are three spin-allowed channels to produce excited O2 molecules with thresholds between 2300 and 2650 A; it is recommended to investigate these dissociative pathways.
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The spectrum produced in the afterglow of an O2-He discharge was studied for the range 4000-8000 A. Lawrence et al. (1977) established that under the appropriate conditions the O2(c 1Sigma u - to X 3Sigma g -) system could be observed in this region. The present study has duplicated these results and has discovered three O2 band systems not previously seen in gas phase laboratory spectra. These systems are C 3Delta u-a 1Delta g, C 3Delta u-X 3Sigma g -, and c 1Sigma u - to a 1Delta g.
Recombination of ground-state oxygen atoms populates six different bound electronic states of molecular oxygen. Of the six optical transitions expected between the three upper states at 4 to 4.5 electron volts and the two lowest states, five have been observed in the afterglow of a conventional helium-oxygen microwave discharge in both (O-16)2 and (O-18)2, three of them for the first time in gas-phase spectra. Generation of these emissions from oxygen atoms in a system free of molecular oxygen establishes that atom recombination is the production mechanism.
Investigations in four different areas were carried out to further our understanding of the chemistry of the atmospheres of Mars and Venus. CO2 photodissociation quantum yields were determined in the 1300-1500 A spectral region by measuring both CO and oxygen atoms. The O(1S) quantum yield was determined for CO2 photodissociation in the 1060-1175 A spectral region. The measurement resolves the differences between two earlier experiments, and demonstrates that the O(1S) yield is unity throughout most of the measured region. The pathways for the quenching of O(1S) by N2O, CO2, H2O and NO were investigated and the source of the Venus nightglow, detected by Venera 9 and 10, was investigated. What appears to be a new O2 band system, was detected although the identity of the transition is not yet evident.
Measurements have been made of the absolute oxygen atom yields from CO2 photolysis at 1470 and 1302-1306 A; in both cases the yield is unity. The CO generation rates have also been measured in these two wavelength regions, and they are proportional to the oxygen atom generation rates; by implication the CO quantum yields are thus also unity. The CO deficiencies observed in earlier work on this subject are probably caused by heterogenous processes.
The first measurements are reported of the reaction pathways for the interaction between oxygen atoms in the 4.19 eV S-1 state, and four molecules, N2O, CO2, H2O, and NO. Distinction is made between three possible paths - quenching to O(D-1), quenching to O(P-3), and chemical reaction. With N2O, the most reasonable interpretation of the data indicates that there no reaction, in sharp contrast with the interaction between O(D-1) and N2O, which proceeds entirely by reaction. Similarly, there is no reaction with CO2. With H2O, the reactive pathway is the dominant one, although electronic quenching is not negligible. With NO, O(D-1) is the preferred product.