Excitation of the oxygen nightglow on the terrestrial planets

A scheme of excitation, quenching, and energy transfer processes in the oxygen nightglow on the Earth, Venus, and Mars has been developed based on the observed nightglow intensities and vertical profiles, measured reaction rate coefficients, and photochemical models of the nighttime atmospheres of the Venus and Mars. The scheme involves improved radiative lifetimes of some band systems, calculated yields of the seven electronic states of O₂ in termolecular association, and rate coefficients of seven processes of electronic quenching of the Herzberg states of O₂, which are evaluated by fitting to the nightglow observations. Electronic quenching of the vibrationally excited Herzberg states by O₂ and N₂ in the Earth's nightglow is a quarter of total collisional removal of the O₂(A, A′) states and a dominant branch for the O₂(c) state. The scheme supports the conclusion by Steadman and Thrush (1994) that the green line is excited by energy transfer from the O₂(A³Σ_u⁺, v≥6) molecules, and the inferred rate coefficient of this transfer is 1.5×10⁻¹¹ cm³ s⁻¹. The O₂ bands at 762 nm and 1.27 μm are excited directly, by quenching of the Herzberg states, and by energy transfer from the O₂(⁵Π_g) state. Quenching of the O₂ band at 762 nm excites the band at 1.27 μm as well. Effective yield of the O₂(a¹Δ_g) state in termolecular association on Venus and Mars is ∼0.7. Quantitative assessments of all these processes have been made. A possible reaction of O₂(c¹Σ_u⁻)+CO is a very minor branch of recombination of CO₂ on Venus and Mars. Night airglow on Mars is calculated for typical conditions of the nighttime atmosphere. The calculated vertical intensity of the O₂ band at 1.27 μm is 13 kR, far below the recently reported detections.     

The altitude dependence of the O2(A3Σu+) vibrational distribution in the terrestrial nightglow

A simple vibrational relaxation model which reproduces the observed altitude integrated vibrational distribution of the Herzberg I bands in the nightglow is used to derive the altitude profiles of the individual vibrational levels at 1 km intervals in the 85–115 km height range. The possible errors associated with using rocket-borne photometer measurements of a limited number of bands in the O₂(A³Σ_u⁺?X³Σ_g^?) system to infer the total Herzberg I emission profile are assessed.     

Mapping of Ozone and Water in the Atmosphere of Mars near the 1997 Aphelion

We present absolute abundances and latitudinal variations of ozone and water in the atmosphere of Mars during its late northern spring (L_s=67.3°) shortly before aphelion. Long-slit maps of the a¹Δ_g state of molecular oxygen (O₂) and HDO, an isotopic form of water, were acquired on UT January 21.6 1997 using a high-resolution infrared spectrometer (CSHELL) at the NASA Infrared Telescope Facility. O₂(a¹Δ_g) is produced by ozone photolysis, and the ensuing dayglow emission at 1.27 μm is used as a tracer for ozone. Retrieved vertical column densities for ozone above ∼20 km ranged between 1.5 and 2.8 μm-atm at mid- to low latitudes (30°S-60°N) and decreased outside that region. A significant decrease in ozone density is seen near 30°N (close to the subsolar latitude of 23.5°N). The rotational temperatures retrieved from O₂(a-X) emissions show a mean of 172±2.5 K, confirming that the sensed ozone lies in the middle atmosphere (∼24 km). The ν₁ fundamental band of HDO near 3.67 μm was used as a proxy for H₂O. The retrieved vertical column abundance of water varies from 3 precipitable microns (pr-μm) at ∼30°S to 24 pr-μm at ∼60°N. We compare these results with current photochemical models and with measurements obtained by other methods.     

The excitation of the 557.7 nm line and Herzberg bands in the nightglow

Measurements of the emission intensities of the 557.7 nm line and Herzberg bands and of O(³P) concentrations carried out on two coordinated rocket flights at South Uist during the night of 8/9 September 1975 are presented. An examination of the 557.7 nm emission and $\text{O}\text{(}{}^3\text{P}\text{)}$ data on the basis of recent data on relevant rate coefficients has shown that the results can be interpreted on the basis of the Barth mechanism for the production of $\text{O}\text{(}{}^1\text{S}\text{)}$ atoms but not the Chapman mechanism. Evidence is provided that the A³Σ⁺_u state of O₂ could be responsible for the $\text{O}\text{(}{}^1\text{S}\text{)}$ production in the Barth mechanism. Values of the rate coefficients involved are deduced from a comparison of the 557.7 nm and Herzberg emission rates.     

The green light of the night sky

The development of the theory of the 5577 Å emission from the upper atmosphere is reviewed. Evidence from both aeronomy and chemical kinetics shows that the Barth mechanism is a much more important source of $\text{O}\text{(}{}^1\text{S}\text{)}$ than in the Chapman process. The molecular oxygen state involved is probably c¹Σ^?_u (the upper state of the Herzberg II band system).     

Rocket measurements of oxygen and nitrogen emissions in the aurora

Altitude distributions of electronically excited atoms and molecules of oxygen and nitrogen in the aurora have been obtained by means of rocket-borne wavelength scanning interference filter photometers launched from Fort Churchill, Manitoba (58.4°N, 94.1°W) on January 23, 1974. Atomic oxygen densities derived from mass spectrometer measurements obtained during the flight are used in conjunction with the volume emission rate ratio of the N₂(C³Π_u?B³Π_g) (0-0) second positive and N₂(A³Σ_u⁺, v = 1?X¹Σ_g⁺) Vegard-Kaplan bands to derive a rate constant for quenching of the N₂(A³Σ_u⁺, v = 1) level with O(³P) of 1.7(±0.8) × 10^?11 cm³ s^?1 These data, together with O den derived from the O₂(b¹Σ_g⁺) state nightglow emission observed during the rocket ascent, suggest that quenching of the N₂(A³Σ_u⁺, v = 1) level by O₂ has a significant positive temperature dependence. The processes involved in the production and loss of the N₂(A³Σ_u⁺) state are considered and energy transfer from the N₂(A³Σ_u⁺) state to O(³P) is found to be a significant source of the OI 5577 Å green line in this aurora at altitudes below 130 km. Emission from the NO(A²Σ⁺?X²Π) gamma bands was not detected, an observation which is consistent with the mass spectrometer data obtained during the flight indicating that the NO density was <10⁸ cm³ at 110 km. On the basis of previous rocket and satellite measurements of the NO gamma bands, energy transfer from the N₂(A³Σ_u⁺) state to NO(X²Π) is shown to be an insignificant source of the gamma bands in aurora. Altitude profiles of the N₂(a¹Π_g?X¹Σ_g⁺) Lyman-Birge-Hopfield band system are presented.     

The solar spectral irradiance and its action in the atmospheric photodissociation processes

A critical analysis has been made of solar irradiance in the spectral region covering wavelengths from 100 nm upwards; the absorption characteristics of molecules of oxygen and ozone have been taken into account with a view to the direct application of the results to atmospheric photochemistry. The absorption of radiation by these molecules results in the photodissociation of both of them in the homosphere, and it also makes possible the penetration of solar radiation from the thermosphere, through the mesosphere and the stratosphere, down to the troposphere.Special attention has been given to each of the following spectral regions: Lyman-alpha radiation at 121.6 nm, the O₂ Schumann-Runge continuum at wavelengths less than 175 nm, the O₂ Schumann-Runge band system from 200 to 175 nm, and the O₂ Herzberg continuum at 242.4 nm. For absorption by ozone, the solar spectrum has been analysed in the following regions: the Hartley band at wavelengths less than 310 nm, the Huggins bands at wavelengths above 310 nm and the visible Chappuis bands. Finally, for the photodissociation of O₃, particular attention has been given to the transition region (300–320 nm) in which there is a change-over from the production of the excited atom O(¹D) to that of the atom in its ground state O(³p).     

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.     

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.     

Excitation of oxygen emissions in the night airglow of the terrestrial planets

The excitation, energy transfer and quenching of O₂ (A³ Σ_u⁺, C³ Δ_u, c¹ Σ_u^?) and O(¹S) are discussed, taking into account laboratory measurements and observations on the airglow of the Earth, Venus and Mars. The excitation of O(¹S) occurs by the Barth mechanism with O₂(c) as a precursor: the rate coefficient is 2.5 × 10^?12 cm³ s^?1 for υ > 0 and 2.5 × 10^?12 exp($\text{?1100}\text{T}$) cm₃ s^?1for υ = 0. The O₂(c) can be formed directly by recombination or by O₂(A) and O₂(C) colliding with other molecules; the O₂(c) yield through quenching of these states is about 0.3 in air and about 1.0 in carbon dioxide. The rate coefficients of some processes that control the molecular oxygen bands and the atomic oxygen green line are estimated.     

Model studies of nitric oxide fluorescence in the earth's backscattered spectrum

Fluorescent emissions from nitric oxide appear imposed upon the Rayleigh backscattered spectrum of the earth's atmosphere between 250 and 300 nm in wavelength. Satellite instruments designed to monitor the global ozone distribution can routinely observe these signals although techniques for exploiting the data are not yet available. Application of a radiative transfer equation developed for an atmosphere including absorption by ozone, molecular scattering, and nitric oxide fluorescence shows the three most prominent NO emissions relative to the 250–300 nm backscattered sunlight to be the (1,4), (1,6), and (0,3) gamma bands. Analysis of the contribution function for each emission band indicates that the fluorescent signals can provide useful information on the magnitude and variability of nitric oxide between 40 and 140 km in altitude.     

Seasonal variations of photochemical tracers at low and middle latitudes on Mars: Observations and models

Mars Express observations give ozone abundances that are smaller than those from the ground-based infrared heterodyne and HST observations at low and middle latitudes. Both ground-based and Mars Express observations of the O₂ dayglow at 1.27 μm, which originates from photolysis of ozone, are in mutual agreement after correction for the local time variability. Therefore a problem appears: whether the MEX ozone data are compatible with (1) the observed O₂ dayglow intensities and (2) the photochemical model by Krasnopolsky [Krasnopolsky, V.A., 2006. Icarus 185, 153-170] within uncertainties of its reaction rate coefficients. That model involves heterogeneous loss of H₂O₂ on water ice and agrees with the observations of the O₂ dayglow, H₂O₂, and the ground-based and HST ozone. The answers are ‘yes’ to both questions. A version of the model is given that fits the MEX ozone as well as the observed O₂ dayglow and H₂O₂. Laboratory studies of two reaction rate coefficients could indicate a preferable version of the model and a preferable set of the ozone data (MEX versus the ground-based and HST). The predicted seasonal behavior of H₂O₂ is different from that in the model by Lefevre et al. [Lefevre, F., Bertaux, J.L., Clancy, R.T., Encrenaz, T., Fast, K., Forget, F., Lebonnois, S., Montmessin, F., Perrier, S., 2008. Nature 454, 971-975], and future observations may help to choose between the models.     

Energy transfer from excited N2 and O2 as a source of O(1S) in the Aurora

It is proposed that energy transfer from excited O₂ contributes to the production of O(¹S) in aurora. An analysis is presented of the OI5577 Å emission in an IBC II⁺ aurora between 90 and 130 km. The volume emission rate of the emission at these altitudes is consistent with the production rate of O(¹S) by energy transfer to O(³P) from N₂ in the A³Σ₂⁺ state and O₂ in the A³Σ_u⁺, C³Δc¹Σ_u^? states, the N₂A state being populated by direct electron impact excitation and B → A cascade and the excited O₂ states by direct excitation. Above the peak emission altitude (~105 km), energy transfer from N₂A is the predominant production mechanism for O(¹S). Below it, the contribution from quenching of the O₂ states becomes significant.     

Mapping of Mars O2 1.27 μm dayglow at four seasonal points

The O₂ dayglow at 1.27 μm is formed by high-altitude ozone on Mars and is a sensitive tracer of Mars photochemistry. Mapping of this dayglow using the IRTF/CSHELL long-slit spectrograph requires the extraction of weak emission lines against a strong continuum of the reflected solar light. Some new tools are suggested to improve the data processing. The observed O₂ dayglow intensities at L_S=67°, 112°, 148°, and 173° show a decrease from late spring (aphelion) to fall equinox by a factor of ≈5 at low latitudes (±30°). This decrease agrees with that predicted by a model of Clancy and Nair (1996, J. Geophys. Res. 101 (12) 12785-12790), although the dayglow intensities are weaker than those based on that model. The measured dayglow variations with latitude are rather low at L_S=67°, 112°, and 148° and unexpectedly high at 173°. The dayglow intensity peaks near noon and is smaller at 9:00 and 16:30 LT by a factor of 2. Some data on the ozone profile near aphelion are obtained from a combination of the dayglow and ozone observations. It is hardly possible to detect the O₂ night airglow at 1.27 μm on Mars using the existing ground-based and on-orbit instruments. The O₂ dayglow intensity as a function of latitude and season from aphelion to fall equinox has been obtained. Our goal is to extend this distribution to the full martian year and get a database for Mars photochemistry to complement the MGS/TES observations of water vapor, atmospheric temperature, and dust and ice aerosol.     

OGO-4 observations of the ultraviolet auroral spectrum

Auroral ultraviolet spectra in the range 1200–3200 A have been obtained by the spectrometer onboard the OGO-4 satellite. Emissions of N₂, H, O and N are readily identified. Atomic and molecular intensities are deduced from the comparison with a synthetic spectrum and compare reasonably well with some previous measurements and calculations. A feature at 2150 A is assigned to the (1-0) NO γ band. Taking into consideration the various excitation mechanisms of NO(A²σ) we propose that the energy transfer from N₂ metastable molecules to oxygen accounts for the excitation of the NO γ bands. In particular, we suggest that the resonant reaction between O₂ and highly metastable N₂(W³Δ) molecules may be a major source of NO(A²σ).     

Excitation of O2 Herzberg Bands in the nightglow

The excitation mechanism for O₂ Herzberg Bands as given by Young and Black (1966) is examined. It is found that O₂ Herzberg Bands are heavily quenched by N atoms, while (0,0) and (0,1) Atmospheric Bands are quenched mainly by CO, NO, O₂ and N₂, NO, O₂ respectively. The emission of Herzberg Bands is found to arise from two layers centred at 80 and 100 km. The rate coefficients of a number of quenching reactions involving atmospheric gases are obtained theoretically.     

Spatial correlation of OH Meinel and O2 infrared atmospheric nightglow emissions observed with VIRTIS-M on board Venus Express

We present the two-dimensional distribution of the O₂ a¹Δ–X³Σ (0–0) band at 1.27 μm and the OH Δv = 1 Meinel airglow measured simultaneously with the Visible and Infrared Thermal Imaging Spectrometer (VIRTIS) on board Venus Express. We show that the two emissions present very similar spatial structures. A cross-correlation analysis indicates that the highest level of correlation is reached with only very small relative shifts of the pairs of images. In spite of the strong spatial correlation between the morphology of the bright spots in the two emissions, we also show that their relative intensity is not constant, in agreement with earlier statistical studies of their limb profiles. We conclude that the two emissions have a common precursor that controls the production of both excited species. We argue that atomic oxygen, which produces O₂ (¹Δ) molecules by three-body recombination and is the precursor of ozone formation, also governs to a large extent the OH airglow morphology through the H + O₃ → OH^* + O₂ reaction.     

Brightness of the O2 atmospheric bands in the daytime thermosphere

The Fabry-Perot interferometer on Dynamics Explorer 2 was used as a low sensitivity photometer to study the O₂ Atmospheric A band during the daytime. A study of the brightness of the emission showed that the assumed source of O₂(b¹Σ_g⁺) in the thermosphere, O(¹D), can account for the observed intensity up to about 250 km but with a significantly different scale height. This combined with an enhanced brightness above this altitude suggests an additional source for this emission.     

The excitation of O2(b1Σg+) in the nightglow

It is proposed that the available measurements of the O₂(b¹Σ_g⁺ ?X³Σ_g^?) atmospheric bands both in the nightglow and in the laboratory indicate that the excitation mechanism is a two-step process rather than the direct three body recombination of atomic oxygen. It is shown that such a two-step mechanism can explain observations of the atmospheric bands both in altitude and intensity.     

Changes in the concentration of mesospheric ozone during the total solar eclipse

Measurements of dayglow radiance of $\text{O}{}_2\text{(}{}^1\text{Δ}{}_{\mathrm{g}}\text{)}$ and OH(7,2) bands are reported. Ground based photometers were used to monitor zenith radiance of 1270 and 694 nm emissions during the total solar eclipse of 16 February 1980. Altitude distribution of 1270 nm intensity was derived from ground based observations. A set of altitude distributions of $\text{O}{}_2\text{(}{}^1\text{Δ}{}_{\mathrm{g}}\text{)}$ were thus obtained throughout the eclipse. These altitude distributions were converted into ozone distributions using the rate equations for formation and loss of ozone and $\text{O}{}_2\text{(}{}^1\text{Δ}{}_{\mathrm{g}}\text{)}$ molecules. Results indicate an increase in the ozone concentration at mid-eclipse. OH(7,2) emission did not show enhancement during totality. This may mean that there was no increase in OH concentration during the eclipse.