Atmospherically Related Studies of O(D-1) and O2 (b'Sigma(sub g, sup +)

For the third year of the grant, we propose to investigate the (beta)'(Sigma)(sub g, sup +). Our earlier value of 0.77 +/- 0.23, which has been used for a long time, should be updated, and the error limits reduced. Current measurements in J. Barker's group at the University of Michigan have assigned a value closer to 0.9, and we will conduct a new evaluation. The goals of this project are to investigate various aspects of the photochemistry of O('D) and O2(beta)'(Sigma)(sub g, sup +) that are of relevance to the photochemistry and energy balance of the terrestrial atmosphere. Over the last six months, we have obtained new sky spectra data files from the Keck telescope via Don Osterbrock at UC Santa Cruz, and now 120 hours of data have been accumulated. Thus, we have been able to make large signal/noise improvements of the O2(b'(Sigma)(sub g, sup +) - X(sup 3)(Sigma)(Sub g, sup -) Atmospheric Band data that we are collecting

Atmospheric Oxygen Photoabsorption

The work conducted on this grant was devoted to various aspects of the photophysics and photochemistry of the oxygen molecule. Predissociation linewidths were measured for several vibrational levels in the O2(B3 Sigma(sub u)(sup -)) state, providing good agreement with other groups working on this important problem. Extensive measurements were made on the loss kinetics of vibrationally excited oxygen, where levels between v = 5 and v = 22 were investigated. Cavity ring-down spectroscopy was used to measure oscillator strengths in the oxygen Herzberg bands. The great sensitivity of this technique made it possible to extend the known absorption bands to the dissociation limit as well as providing many new absorption lines that seem to be associated with new O2 transitions. The literature concerning the Herzberg band strengths was evaluated in light of our new measurements, and we made recommendations for the appropriate Herzberg continuum cross sections to be used in stratospheric chemistry. The transition probabilities for all three Herzberg band systems were re-evaluated, and we are recommending a new set of values

A Study of Pioneer Venus Nightglow Spectra

The work performed during the 12-month period of this contract involved: (1) further analysis of latitudinal variations in the Venusian NO nightglow intensity from PVOUVS data; (2) corrections made to the input data for the VTGCM model, relating specifically to a factor of three increase in the three-body recombination rate coefficient of N + O; (3) consideration of limits on the rate of reaction of N-atoms with CO2; (4) consideration of the Venusian equivalent of the terrestrial hot N-atom reaction for NO production; and (5) successful location of video images of meteor trails from space, for the purpose of making a comparison with the meteor trail that we have hypothesized as an explanation of intense UV spectra observed on a particular Pioneer Venus (PV) orbit

Predissociation in N2(C'4, 1 Sigma u +) and other N2 states and its importance in the atmospheres of Titan and Triton

The objectives of this program are to further the understanding of the upper atmospheres of Titan, Triton, and the Earth in terms of the observed emissions of the 13-14 eV states of N2. These states are generated at quite high rates, yet very little emission is observed from them. The reasons are complex, involving resonance trapping and predissociation, and it is desired to quantify the effects of predissociation, particularly on the c(sub 4)' 1 Sigma(sub u),(sup +) state of N2. Earlier experiments had indicated that predissociation of the c(sub 4)' state was of little importance, yet over the last two years a growing body of evidence has shown that for levels above v = 2, predissociation is in fact a major process. It is the v = 0 level for which production by electron bombardment and photoexcitation is highest, and so it has been most important to evaluate the effects of predissociation on this particular level. The goal has been to target c(sub 4)' (v = 0) for a thorough analysis, in which both the extent of predissociation as a function of rotational level and the atomic product branching ratio, where the only possible products are N(4S) + N(4S) and N(2D) + N(4S), are determined. For the first year of funding, the intention was to demonstrate two-photon excitation of the intermediate N2(a(sup 1) Pi(sub g)) state, so that the gap to the 13 eV energy region could be bridged, and then use a second laser to reach the c(sub 4)' state itself

An investigation of the processes controlling ozone in the upper stratosphere

Photolysis of vibrationally excited oxygen produced by ultraviolet photolysis of ozone in the upper stratosphere is incorporated into the Lawrence Livermore National Laboratory 2-D 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 upon recent information on vibrational distributions of excited oxygen and upon preliminary studies of energy transfer from the excited oxygen. When the energy transfer rate constants of previous work are assumed, increases in model ozone concentrations of up to 40 percent in the upper stratosphere are found, and the ozone concentrations of the model agree with measurements, including data from the Upper Atmosphere Research Satellite. However, the increase is about 0.4 percent when the larger energy transfer rate constants suggested by more recent experimental work are applied in the model. This indicates the importance of obtaining detailed information on vibrationally excited oxygen properties to evaluation of this process for stratospheric modelling

The 557.7 nm Oxygen Green Line in the Venus Nightglow

Observations of Venus in 1999 from the Keck I telescope in Hawai’i showed that the oxygen green line can be a relatively strong nightglow feature (~150 R), rivaling the intensity of the terrestrial green line [Slanger et al., 2001]. The emission was not seen in two orbital missions - the Venera 9/10 study, in which the O2 Herzberg II bands were first observed [Krasnopolsky et al., 1976], and more recently, the Venus Express (VIRTIS) measurements [Garcia-Muñoz et al., 2009]. Repeated ground-based measurements of the green line have found an intensity varying strongly from apparition to apparition [Slanger et al., 2006]; it has so far not reached the emission level seen in November 1999, at close to solar maximum. We assume that the source of the green line is either O-atom recombination in the mesosphere, or O2+ dissociative recombination (DR) in the ionosphere, the two main terrestrial processes. The 2007-2008 data used in the VIRTIS/VEX study were co-added over many orbits, during a period when ground-based observations indicated a moderate (~50 R) green line intensity. In this presentation we consider the argument for a mesospheric vs an ionospheric source. A mesospheric source would be strongly modulated by the temperature-dependent quenching of O(1S) by CO2. An ionospheric source could be interpreted in terms of ion densities [Pätzold et al., 2007]. Although the O(1D) yield is much larger than that of O(1S) from O2+ DR, O(1D) quenching by CO2 would preclude its observation and indeed, no oxygen red line was seen in 1999 when the green line intensity was at its peak. [Supported by NASA Planetary Astronomy] Garcia-Munoz, A., et al., J. Geophys. Res., (submitted, 2009).Krasnopolsky, V.A. et al., Cosmic Research, 1976.Patzold, M. et al., Nature, doi:10.1038/nature06239, 2007Slanger, T.G., et al., Science, 2001.Slanger, T.G., et al., Icarus, 2006

The 557.7 nm Oxygen Green Line in the Venus Nightglow

Observations of Venus in 1999 from the Keck I telescope in Hawai’i showed that the oxygen green line can be a relatively strong nightglow feature (~150 R), rivaling the intensity of the terrestrial green line [Slanger et al., 2001]. The emission was not seen in two orbital missions - the Venera 9/10 study, in which the O2 Herzberg II bands were first observed [Krasnopolsky et al., 1976], and more recently, the Venus Express (VIRTIS) measurements [Garcia-Muñoz et al., 2009]. Repeated ground-based measurements of the green line have found an intensity varying strongly from apparition to apparition [Slanger et al., 2006]; it has so far not reached the emission level seen in November 1999, at close to solar maximum. We assume that the source of the green line is either O-atom recombination in the mesosphere, or O2+ dissociative recombination (DR) in the ionosphere, the two main terrestrial processes. The 2007-2008 data used in the VIRTIS/VEX study were co-added over many orbits, during a period when ground-based observations indicated a moderate (~50 R) green line intensity. In this presentation we consider the argument for a mesospheric vs an ionospheric source. A mesospheric source would be strongly modulated by the temperature-dependent quenching of O(1S) by CO2. An ionospheric source could be interpreted in terms of ion densities [Pätzold et al., 2007]. Although the O(1D) yield is much larger than that of O(1S) from O2+ DR, O(1D) quenching by CO2 would preclude its observation and indeed, no oxygen red line was seen in 1999 when the green line intensity was at its peak. [Supported by NASA Planetary Astronomy] Garcia-Munoz, A., et al., J. Geophys. Res., (submitted, 2009).Krasnopolsky, V.A. et al., Cosmic Research, 1976.Patzold, M. et al., Nature, doi:10.1038/nature06239, 2007Slanger, T.G., et al., Science, 2001.Slanger, T.G., et al., Icarus, 2006

Chemical Origins of the Mars Ultraviolet Dayglow

Airglow optical emissions from planetary atmospheres provide remotely observable signatures of atmospheric composition, energy deposition processes, and the resulting chemical reactions. We may one day be able to detect airglow emissions from extrasolar planets. Reliable interpretation requires quantitative understanding of the energy sources and chemical mechanisms that produce them. The ultraviolet dayglow observations by the Mariner 6 and 7 (1969) and Mariner 9 (1971–72) motivated numerous modeling studies and laboratory experiments. The most obvious source reaction is photodissociation and photoionization of ambient CO2, which is known in the laboratory to produce the four strong dayglow emitting states: hν + CO2 → O(1S), CO(a3Π), CO+2(A2Πu & B2Σ+u) If this simplest of models were sufficient, then the high altitude dayglow emissions would all share the same scale height, which would be that of CO2. The few Mariner dayglow observations provide weak statistics. Addition of 4 months of Mars Express dayglow data, and including radio occultation and mass spectrometry data from other missions, have made the analyses and conclusions more robust. The CO(a3Π) and CO+2(B2Σ+u) dayglow altitude profiles are consistent with the first source reaction. In contrast, the O(1S) dayglow scale heights are much larger and are consistent with a second source reaction: O+2 + e− → O(1S) Both sets of scale heights change with respect to solar activity roughly as suggested by modeling studies

Chemical Origins of the Mars Ultraviolet Dayglow

Airglow optical emissions from planetary atmospheres provide remotely observable signatures of atmospheric composition, energy deposition processes, and the resulting chemical reactions. We may one day be able to detect airglow emissions from extrasolar planets. Reliable interpretation requires quantitative understanding of the energy sources and chemical mechanisms that produce them. The ultraviolet dayglow observations by the Mariner 6 and 7 (1969) and Mariner 9 (1971–72) motivated numerous modeling studies and laboratory experiments. The most obvious source reaction is photodissociation and photoionization of ambient CO2, which is known in the laboratory to produce the four strong dayglow emitting states: hν + CO2 → O(1S), CO(a3Π), CO+2(A2Πu & B2Σ+u) If this simplest of models were sufficient, then the high altitude dayglow emissions would all share the same scale height, which would be that of CO2. The few Mariner dayglow observations provide weak statistics. Addition of 4 months of Mars Express dayglow data, and including radio occultation and mass spectrometry data from other missions, have made the analyses and conclusions more robust. The CO(a3Π) and CO+2(B2Σ+u) dayglow altitude profiles are consistent with the first source reaction. In contrast, the O(1S) dayglow scale heights are much larger and are consistent with a second source reaction: O+2 + e− → O(1S) Both sets of scale heights change with respect to solar activity roughly as suggested by modeling studies