The dissociation of OH and OD in comets by solar radiation

The radiative lifetimes of cometary OH are calculated as a function of the heliocentric velocity of the comet and the velocity distributions of the product atoms are determined. At a distance of 1 AU from the Sun, the lifetimes vary between 1.2×10⁵ and 1.9×10⁵ sec at solar minimum and between 1.0×10⁵ and 1.4×10⁵ sec at solar maximum, depending upon velocity. Continuous absorption into the repulsive 1²Σ^- state is major destruction path. The calculated lifetimes are generally consistent with the lifetimes inferred from observations, but suggest some elaboration of the models is necessary. Photodissociation of OH produces a low-velocity component of hydrogen atoms at 8 km sec^?1 relative to the parent OH molecule and a high-velocity component between 17 and 27 km sec^?1. Photodissociation of OH leads to metastable O(¹D) and O(¹S) and is an additional source of the red and green line emission of atomic oxygen. The lifetime of OD is estimated to be about 4.3× 10⁵ sec at solar minimum and 2.6×10⁵ sec at solar maximum so that the OD/OH ratio in comets is enhanced relative to the HDO/H₂O production ratio by a factor between 2 and 3. Photodissociation of OD produces only high-velocity D atoms with a mean value of 17 km sec^?1.     

Atomic oxygen distribution in the Venus mesosphere from observations of O2 infrared airglow by VIRTIS-Venus Express

This VIRTIS instrument on board Venus Express has collected spectrally resolved images of the Venus nightside limb that show the presence of the (0,0) band of the infrared atmospheric system of O₂ at 1.27 μm. The emission is produced by three-body recombination of oxygen atoms created by photodissociation of CO₂ on the dayside. It is consistently bright so that emission limb profiles can be extracted from the images. The vertical distribution of O₂() may be derived following Abel inversion of the radiance limb profiles. Assuming photochemical equilibrium, it is combined with the CO₂ vertical distribution to determine the atomic oxygen density. The uncertainties on the O density caused by the Abel inversion reach a few percent at the peak, increasing to about 50% near 120 km. We first analyze a case when the CO₂ density was derived from a stellar occultation observed with the SPICAV spectrometer simultaneously with an image of the O₂ limb airglow. In other cases, an average CO₂ profile deduced from a series of ultraviolet stellar occultations is used to derive the O profile, leading to uncertainties on the O density less than 30%. It is found that the maximum O density is generally located between 94 and 115 km with a mean value of 104 km. It ranges from less than 1×¹⁰¹¹ to about 5×¹⁰¹¹ cm⁻³ with a global mean of 2.2×¹⁰¹¹ cm⁻³. These values are in reasonable agreement with the VIRA midnight oxygen profile. The vertical O distribution is generally in good agreement with the oxygen profile calculated with a one-dimensional chemical-diffusive model. No statistical latitudinal dependence of the altitude of the oxygen peak is observed, but the maximum O density tends to decrease with increasing northern latitudes. The latitudinal distribution at a given time exhibits large variations in the O density profile and its vertical structure. The vertical oxygen distribution frequently shows multiple peaks possibly caused by waves or variations in the structure of turbulent transport. It is concluded that the O₂ infrared night airglow is a powerful tool to map the distribution of atomic oxygen in the mesosphere between 90 and 115 km and improve future Venus reference atmosphere models.     

The quenching of OH1 in the atmosphere

The intensity distribution of the OH Meinel bands in the airglow has been derived from the minor constituent profiles of Moreels et al. (1977). It has been shown that there is good agreement between the observed and calculated intensity distribution for excitation through the hydrogen-ozone reaction and quenching of the excited state by reaction with atomic oxygen and through vibrational relaxation. The rate constants for vibrational relaxation have been derived and are found to be vibrational level dependent; for the ν = 7 level, the peak value, the rate constant is 5.8 × 10^?12cm³s^?1.     

A measurement of the O2(b1Σg+−X3Σg−) atmospheric band and the OI(1S) green line in the nightglow

Simultaneous measurements of the nightglow profiles of the O₂(b¹Σ_g⁺?X³Σ_g^?) A-band, the atomic oxygen green line and the OH (8?3) Meinel band are presented. The altitude profiles are used to determine both the excitation mechanisms for the oxygen emissions and the atomic oxygen altitude distribution. It is shown that the measurements are consistent with a green line excitation through the Barth mechanism and that the molecular oxygen emission is excited through oxygen recombination and the reaction between OH¹ and atomic oxygen. The derived atomic oxygen concentrations,6.2 × 10¹¹cm^?3at 98km, are consistent with the Jacchia (1971) model.     

Direct measurement of conjugate photoelectrons and predawn 630 nm airglow

A sounding rocket was flown during the predawn on 17 January, 1976 from Uchinoura, Japan, to measure directly the behaviour of the conjugate photoelectrons at magnetically low latitudes. On board the rocket were an electron energy analyzer, 630 nm airglow photometer, and plasma probes to measure electron density and temperature. The incoming flux of the photoelectrons was measured in the altitude range between 210 and 340 km. The differential flux at the top of the atmosphere was determined to be $\text{F = (1.3 ± 0.4) × 10}{}^{11}\text{exp}\text{[?}\text{E(}\text{eV}\text{)}\text{12}\text{]}$ electron · m^?2 · sr^?1 · s^?1 in the energy range 10 ? E ? 50 eV. The emission rate of the 630 nm airglow was observed in the altitude range between 90 and 360 km. The apparent emission rate observed at 80 km was 32 ± 5 R. From a theoretical calculation of the optical excitation rate using the observed electron flux data along with a model distribution of atomic oxygen, it was estimated that more than 65% of the emission could be produced by direct impact of the photoelectrons with atomic oxygen in the thermosphere between 200 and 360 km. Using the observed electron density and the model distribution of oxygen molecules the residual of the emission was ascribed to the excitation of O(¹D) through dissociative recombination, $\text{O}{}_2{}^{\mathrm{+}}\text{+}\text{e}\text{→}\text{O}{}^1\text{+}\text{O}{}^7$. The direct collisional excitation by ambient electrons is estimated to be negligibly small at the level of observed electron temperature.     

A global study of O2(1Δg) airglow: Day and twilight

Aircraft measurements of $\text{O}{}_2\text{(}{}^1\text{Δ}{}_{\mathrm{g}}\text{)}$ emission made over a 10-yr period provide information on the variation of ozone with latitude and season in the altitude region 50–90 km. Between 50 and 70 km there appears to be little variation (< ± 25%) whereas the abundance between 80 and 90 km exhibits a large seasonal change north of 30°N and much less at lower latitude. At mid and high latitude the column abundance above ～ 80 km changes from ? 1 × 10¹⁴ cm^?2 in summer to about 3 × 10¹⁴ cm^?2 in winter. There are occasional enhancements in both the day and twilight airglow which almost always occur in association with auroral activity or, at least, where such activity is statistically most likely. These enhancements appear to reflect a corresponding increase in the ozone mixing ratio in the upper stratosphere. While the gradient in ozone mixing ratio with latitude is generally small at altitudes between 50 and 90km there are occasions when a temporary latitude structure can be seen, particularly above 80 km.     

Thermospheric no profiles observed at the diminishing phase of solar cycle 21

Two density profiles of the thermospheric nitric oxide were obtained by means of the γ(1,0) band airglow measured with rocket-home radiometers flown from Uchinoura, Japan (31°N) at around autumnal equinoxes in 1982 and 1983. The peak densities were found at altitudes of 105–110 km and are 9 × 10⁷ and 7 × 10⁷ cm⁻³, respectively. They are well reproduced by the variation of solar activity in terms of a one-dimensional photochemical-diffusive model, but the densities above 140 km under moderate solar activity differ considerably from the model prediction. A similar discrepancy has already been found in the NO density profile obtained by our previous experiment at solar maximum. These discrepancies infer a possibility either that our understanding of thermospheric nitrogen chemisty includes a serious error, or that the meridional circulation affects considerably the NO density profile even at altitudes above 140 km and at low latitudes.     

Atomic oxygen concentration from the measurement of the [OI] 5577 Å emission of the airglow

The rocketborne measurements of the [OI] 5577 Å emission reported here are from an attempt made to determine the distribution of atomic oxygen from the sequential measurements of the brightness of the [OI] green line emission and the chemiluminescence of nitric oxide. Our results show that a) this emission originates from two layers, one around 100 km and the other above 150 km, and b) the peak concentrations of atomic oxygen determined from the Chapman and the Barth mechanism are 7 × 10¹¹ and 9 × 10¹⁰ cm⁻³ respectively. Though the peak concentrations differ from each other by an order of magnitude, the profiles from the two mechanisms are very much similar in shape. With the new rate coefficient as 1· 5 × 10⁻³³ cm⁶/sec, the Chapman mechanism is adequate for explaining the [OI] green line emission around 100 km.     

Equatorial ozone profiles from the solar maximum mission—a comparison with theory

The u.v. spectrometer polarimeter on the Solar Maximum Mission has been utilized to measure mesospheric ozone vs altitude profiles by the technique of solar occultation. Sunset data are presented for 1980, during the fall equinoctal period within ± 20° of the geographic equator. Mean O₃, concentrations are 4.0 × 10¹⁰ cm^?3at 50 km, 1.6 × 10¹⁰ cm^?3 at 55 km. 5.5 × 10⁹ cm^?3 at 60 km and 1.5 × 10⁹ cm^?3 at 65 km. Som profiles exhibit altitude structure which is wavelike. The mean ozone profile is fit best with the results of a time-dependent model if the assumed water vapor mixing ratio employed varies from 6 ppm at 50 km to 2–4 ppm at 65 km.     

Rocket observation of conjugate photoelectrons in the predawn ionosphere

Photoelectron flux in the energy range 6–70 eV coming from the sunlight conjugate ionosphere has been measured directly by the rocket borne low energy electron spectrometer in the altitude region of 210–350 km. Pitch angle distribution of the measured flux is nearly isotropic, the flux decreasing slightly with pitch angle. The photoelectron fluxes measured at 350 km at the energies of 15 and 30 eV are 3 × 10⁶ and 1 × 10⁶ (cm² s str eV)^?1 respectively which decrease to 1 × 10⁶ and 1 × 10⁵ at 250 km at the same energies. These values are consistent with the vertical profile of the 630 nm airglow intensity measured simultaneously. The fluxes obtained near apogee show peaks in the range 20–30 eV which also appear in the daytime photoelectron flux, indicating reduced loss of electrons during the passage from the conjugate ionosphere through the plasmasphere at the low geomagnetic latitude where observation was made. Photoelectron fluxes observed below the apogee height are compared to the calculated fluxes to investigate the interaction of electrons with the atmospheric species during the passage in the ionosphere. Calculated fluxes obtained by using continuous slowing-down approximation and neglecting pitch angle scattering are in good agreement with the observations although there still remain disagreements in detailed comparison which may be ascribed to the assumptions inherent in the calculation and/or to the uncertainties of the input data for the calculation.     

An Antarctic no density profile deduced from the gamma band airglow

The nitric oxide density profile between the altitudes 72 and 120 km was obtained by means of the airglow γ(1, 0) band measured with a rocket-borne radiometer flown at Syowa Station (69°S, 40°E). The NO density was found to have two peaks with a value of 1.5× 10⁸cm^?3 at 90 and 110 km, and is much larger than those in the middle and low latitudes. Because of a long lifetime of NO in the mesosphere, the observed NO enhancement may be due to the after-effect of the particle precipitation event which occurred within the half day before, despite no polar disturbance during the rocket flight.     

Io's sodium emission cloud

Strong evidence that Io's sodium emission is due to resonant scattering is given by our observations which show a monotonic increase of emission intensity with residual solar intensity. In addition we detected no emission during three eclipse observations of Io. We propose a resonant scattering model with two spacial components comprising an optically thick atmosphere extending 10³ km above Io's surface surrounded by an optically thin cloud which forms a partial torus around Jupiter. In this model a flux of 10⁷ cm^?2 sec^?1 sodium atoms are sputtered from Io's surface by heavy energetic ions which are accelerated in a plasma sheath around Io. The atoms sputtered from the surface collide with atoms in Io's atmosphere so the equipartition of kinetic energy is established. The total sodium abundance is about 3 × 10¹³ cm^?2. During Io's day, sodium and other atmospheric constituents are ionized, giving rise to the ionosphere observed by Pioneer 10. Atoms escape by means of Jeans escape from the critical level, which is at the top of the atmosphere and the base of the cloud. We have observed sodium emission 6arcsec (6 Io diameters) above and below Io's orbital plane and 23arcsec toward Jupiter in Io's orbital plane. No emission was detected at maximum elongation 180° from Io. We interpret these results to mean that atoms escaping from Io form a partial torus whose thickness is about 12 arcsec and whose length is at least one-fifth of Io's orbital circumference.     

Atomic oxygen on the Venus nightside: Global distribution deduced from airglow mapping

The Visible and Infra-Red Thermal Imaging Spectrometer (VIRTIS) instrument on board the Venus Express spacecraft has measured the O₂(a¹Δ) nightglow distribution at 1.27 μm in the Venus mesosphere for more than two years. Nadir observations have been used to create a statistical map of the emission on Venus nightside. It appears that the statistical 1.6 MR maximum of the emission is located around the antisolar point. Limb observations provide information on the altitude and on the shape of the emission layer. We combine nadir observations essentially covering the southern hemisphere, corrected for the thermal emission of the lower atmosphere, with limb profiles of the northern hemisphere to generate a global map of the Venus nightside emission at 1.27 μm. Given all the O₂(a¹Δ) intensity profiles, O₂(a¹Δ) and O density profiles have been calculated and three-dimensional maps of metastable molecular and atomic oxygen densities have been generated. This global O density nightside distribution improves that available from the VTS3 model, which was based on measurements made above 145 km. The O₂(a¹Δ) hemispheric average density is 2.1 × 10⁹ cm^?3, with a maximum value of 6.5 × 10⁹ cm^?3 at 99.2 km. The O density profiles have been derived from the nightglow data using CO₂ profiles from the empirical VTS3 model or from SPICAV stellar occultations. The O hemispheric average density is 1.9 × 10¹¹ cm^?3 in both cases, with a mean altitude of the peak located at 106.1 km and 103.4 km, respectively. These results tend to confirm the modeled values of 2.8 × 10¹¹ cm^?3 at 104 km and 2.0 × 10¹¹ cm^?3 at 110 km obtained by Brecht et al. [Brecht, A., Bougher, S.W., Gérard, J.-C., Parkinson, C.D., Rafkin, S., Foster, B., 2011a. J. Geophys. Res., in press] and Krasnopolsky [Krasnopolsky, V.A., 2010. Icarus 207, 17–27], respectively. Comparing the oxygen density map derived from the O₂(a¹Δ) nightglow observations, it appears that the morphology is very different and that the densities obtained in this study are about three times higher than those predicted by the VTS3 model.     

Lightnings and nitric oxide on Venus

In an updating of energy characteristics of lightnings on Venus obtained from Venera-9 and -10 optical observations, the flash energy is given as 8 × 10⁸ J and the mean energy release of lightnings is 1 erg cm^?2 s which is 25 times as high as that on the Earth. Lightnings were observed in the cloud layer. The stroke rate in the near-surface atmosphere is less than 5 s^?1 over the entire planet if the light energy of the stroke exceeds 4 × 10⁵ J and less than 15 s^?1 for (1–4) × 10⁵ J.The average NO production due to lightnings equals 5 × 10⁸ cm^?2 s^?1, the atomic nitrogen production is equal to 7 × 10⁹ cm^?2s^?1,the N flux toward the nightside is 3.2 × 10⁹ cm^?2s^?1, the number densities [N] = 3 × 10⁷cm^?3 and [NO] = 1.8 × 10⁶cm^?3 at 135 km. Almost all NO molecules in the upper atmosphere vanish interacting with N and the resulting NO flux at 90-80 km equals 5 × 10⁵cm^?2s^?1, which is negligibly small as compared with lightning production. If the predissociation at 80–90 km is regarded as the single sink of NO, its mixing ratio, f_NO, is 4 × 10^?8, for the case of a surface sink f_NO = 0.8 × 10^?9 at 50 km. Excess amounts, $\text{f}{}_{\mathrm{<mtext>NO</mtext>}}\text{? 4 × 10}{}^{\mathrm{?8}}$, may exist in the thunderstorm region.     

Some problems in Venus' aeronomy

Models are presented for the height distribution of various photochemically active gases in Venus' upper atmosphere. Attention is directed to the chemistry and vertical transport of odd hydrogen (H, OH, HO₂, H₂O₂), odd oxygen (O, O₃), free chlorine (Cl, ClO, ClOO, Cl₂), CO, O₂, H₂ and H₂O. Supply of O₂ may play a limiting role in the formation of a possible H₂SO₄ cloud on Venus. The supply rate is influenced by both chemical and dynamical processes in the stratosphere, and an analysis of recent spectroscopic data for O₂ implies a lower limit to the appropriate eddy coefficient of about 3 × 10⁵ cm²/sec. The abundances of thermospheric O and CO are determined largely by vertical mixing, and an analysis of Mariner 10 measurements of Venus' Lyman α airglow suggests that the eddy coefficient in the lower thermosphere may be as large as 5 × 10⁷cm²sec. The corresponding values for the mixing ratios of O and CO at the ionospheric peak are approximately 1 per cent. The Lyman α data could be reconciled with larger values for thermospheric O, and smaller values for the vertical eddy coefficient, if non-thermal loss processes were to play a dominant role in hydrogen escape, and if the corresponding flux were to exceed 10⁷ atoms/cm²/sec. A sink of this magnitude would imply major depletion of Venus' atmospheric water over geologic time, and would appear to require mixing ratios of H₂O in the lower atmosphere in excess of 4 × 10^?4. The extensive component to the Lyman α emission measured by Mariner 5 may be due to resonance scattering of sunlight by hot atoms formed by charge transfer with O⁺. The H scale height, therefore, may reflect the temperature of positive ions in Venus' topside ionosphere.     

The measurement of ozone concentrations at high latitude during the twilight

The ozone height profile in the Arctic, at the end of the winter, has been measured up to an altitude of 100 km using a combined solar occultation and 1.27 μ oxygen emission technique. The typical two layer structure has been observed with a high altitude minimum near 80 km and a maximum at 86 km. The measured concentration in this ozone bulge was 5.1 × 10⁷cm^?3, typical of that measured at 52°N for the summer months. It is suggested that this reduced ozone concentration may have been associated with a stratospheric warming event that was in progress at the time of the measurement.     

Martian isotopic ratios and upper limits for possible minor constituents as derived from Mariner 9 infrared spectrometer data

The Mariner 9 infrared spectrometer obtained data over a large part of Mars for almost a year beginning late in 1971. Mars' infrared emission spectrum was measured from 200 to 2000 cm^?1 with an apodized resolution of 2.4 cm^?1. No significant deviation from terrestrial ratios of carbon (¹²C/¹³C) or oxygen (¹⁶O/¹⁸O; ¹⁶O/¹⁷O) isotopes was observed on Mars. The ¹²C/¹³C isotopic ratio was found to be terrestrial with an uncertainty of 15%. Upper limits have been calculated for several minor constituents. With an effective noise equivalent radiance of 1.2 × 10^?9 W cm^?2 sr^?1/cm^?1, new upper limits in centimeter-atmospheres of 2 × 10^?5 for C₂H₂, 4 × 10^?3 for C₂H₄, 3 × 10^?3 for C₂H₆, 2 × 10^?4 for CH₄, 1 × 10^?3 for N₂O, 1 × 10^?4 for NO₂, 4 × 10^?5 for NH₃, 1 × 10^?3 for PH₃, 7 × 10^?4 for SO₂, and 1 × 10^?4 for OCS have been derived.     

Airglow on Mars: Some model expectations for the OH Meinel bands and the O2 IR atmospheric band

This work presents model calculations of the diurnal airglow emissions from the OH Meinel bands and the O₂ IR atmospheric band in the neutral atmosphere of Mars. A time-dependent photochemical model of the lower atmosphere below 80 km has been developed for this purpose. Special emphasis is placed on the nightglow emissions because of their potential to characterize the atomic oxygen profile in the 50-80 km region. Unlike on Earth, the OH Meinel emission rates are very sensitive to the details of the vibrational relaxation pathway. In the sudden death and collisional cascade limits, the maximum OH Meinel column intensities for emissions originating from a fixed upper vibrational level are calculated to be about 300 R, for transitions v^′=9→v^′?8, and 15,000 R, for transitions v^′=1→v^′=0, respectively. During the daytime the 1.27 μm emission from O₂(), primarily formed from ozone photodissociation, is of the order of MegaRayleighs (MR). Due to the long radiative lifetime of O₂(), a luminescent remnant of the dayglow extends to the dark side for about two hours. At night, excited molecular oxygen is expected to be produced through the three body reaction O + O + CO₂. The column emission of this nighttime component of the airglow is estimated to amount to 25 kR. Both nightglow emissions, from the OH Meinel bands and the O₂ IR atmospheric band, overlap in the 50-80 km region. Photodissociation of CO₂ in the upper atmosphere and the subsequent transport of the atomic oxygen produced to the emitting layer are revealed as key factors in the nightglow emissions from these systems. The Mars 5 upper constraint for the product [H][O₃] is revised on the basis of more recent values for the emission probabilities and collisional deactivation coefficients.     

On the structure of Mars' atmosphere at 120–220 km

Altitude dependences of [CO₂] and [CO₂⁺] are deduced from Mariner 6 and 7 CO₂⁺ airglow measurements. CO₂ densities are also obtained from n_e radio occultation measurements. Both [CO₂] profiles are similar and correspond to the model atmosphere of Barth et al. (1972) at 120 km, but at higher altitudes they diverge and at 200–220 km the obtained [CO₂] values are three times less the model. Both the airglow and radio occultation observations show that a correction factor of 2.5 should be included into the values for solar ionization flux given by Hinteregger (1970). The ratio of [CO₂⁺]/n_e is 0.15–0.2 and, hence, [O]/[CO₂] is ～3% at 135 km. An atmospheric and ionospheric model is developed for 120–220 km. The calculated temperature profile is characterized by a value of T ≈ 370°K at h ? 220 km, a steep gradient (～2°/km) at 200-160 km, a bend in the profile at 160 km, a small gradient (～0.7°/km) below and a value of T ≈ 250°K at 120 km. The upper point agrees well with the results of the Lyman-α measurements; the steep gradient may be explained by molecular viscosity dissipation of gravity and acoustical waves (the corresponding energy flux is 4 × 10^?2 erg cm^?2sec^?1 at 180 km). The bend at 160 km may be caused by a sharp decrease of the eddy diffusion coefficient and defines K ≈ 2 × 10⁸cm²sec^?1; and the low gradient gives an estimate of the efficiency of the atmosphere heating by the solar radiation as ? ≈ 0.1.     

Altitude profile of H in the atmosphere of Venus from Lyman α observations of Venera 11 and Venera 12 and origin of the hot exospheric component

Two extreme ultraviolet (EUV) spectrophotometers flown in December 1978 on Venera 11 and Venera 12 measured the hydrogen Lyman α emission resonantly scattered in the atmosphere of Venus. Measurements were obtained across the dayside of the disk, and in the exosphere up to 50,000 km. They were analyzed with spherically symmetric models for which the radiative transfer equation was solved. The H content of the Venus atmosphere varies from optically thin to moderately thick regions. A shape fit at the bright limb allows one to determine the exospheric temperature T_c and the number density n_c independently of the calibration of the instrument or the exact value of the solar flux. The dayside exospheric temperature was measured for the first time in the polar regions, with T_c = 300 ± 25°K for Venera 11 (79°S) and T_c = 275 ± 25°K (59°S) for Venera 12. At the same place, the density is n_c = 4_?2⁺³ × 10⁴ atom.cm^?3, and the integrated number density N_t from 250 to 110 km (the level of CO₂ absorption) is 2.1 × 10¹² atom.cm^?2, a factor of 3 to 6 lower than that predicted in aeronomical models. This probably indicates that the models should be revised in the content of H-bearing molecules and should include the effect of dynamics. Across the disk the value of N_t decreases smoothly with a total variation of two from the morning side to the afternoon side. Alternately it could be a latitude effect, with less hydrogen in the polar regions. The nonthermal component if clearly seen up to 40,000 km of altitude. It is twice as abundant as at the time of Mariner 10 (solar minimum). Its radial distribution above 4000 km can be simulated by an exospheric distribution with T = 10³⁰K and n = 10³ atom.cm^?3 at the exobase level. However, there are less hot atoms between 2000 and 4000 km than predicted by an ionospheric source. A by-product of the analysis is a determination of a very high solar Lyman α flux of 7.6 × 10¹¹ photons (cm² sec Å)^?1 at line center (1 AU) in December 1978.