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.     

Effects of ion excitation on charge transfer reactions of the Mars, Venus, and Earth ionospheres

The absolute reaction cross sections and reaction rate coefficients as a function of photoionisation energy for 25 ion-molecule reactions (charge transfer reactions except for one) have been measured between the most abundant species present as ions or neutral in the Mars, Venus and Earth ionospheres: O₂, N₂, NO, CO, Ar and CO₂.This study shows the strong influence of electronic as well as vibrational internal energy on most ion-molecule reactions. In particular endothermic charge transfer reactions are driven by electronic excitation of O₂⁺ and NO⁺ ions in their a⁴Π_u and a³Σ⁺ metastable states, respectively. Moreover, it is shown that lifetimes of these metastable states are sufficient to survive the mean free path in the lowest part of ionospheres and therefore express their enhanced reactivity. The reactions of O₂⁺ with NO as well as the reactions of CO₂⁺ with NO, O₂, CO and to a less extent N₂ are driven by vibrational excitation. N₂⁺ and CO⁺ reactions vary much less with photon energy than the other ones, except for the case of reactions with Ar. The effects of the molecular ion internal energy content on their reactivity must be included in the ionospheric models for most of the reactions investigated in the present work. It is also the case for the effect of collision energy on the CO⁺+M reactions as we expect that a significant proportion of these CO⁺ could be produced with translational energy by dissociation of doubly charged CO₂²⁺, in particular in the Mars ionosphere. Recommended effective rate constant values are given as a function of VUV photon energy.     

Ionospheric composition in SAR-arcs

The high electron temperatures existing within SAR-arcs can result in enhanced vibrational excitation of atmospheric N₂ molecules and, as a consequence, increase the rate coefficient of the reaction, O⁺ + N₂ → NO⁺ + N. This results in a change in the relative abundance of O⁺ and NO⁺+ in the SAR-arc region compared with that in the undisturbed ionosphere. Theoretical ion density profiles were computed by a triple ion analysis solving the mass, momentum and energy equations for O⁺, NO⁺ and O⁺₂ ions self-consistently. Although the electron temperature dependence of the recombination rate of NO⁺ is not well known, the results show that for a range of expected recombination rates NO⁺ still remains the dominant ion up to ca. 320 km at night within a bright SAR-arc. Studies were also made of the relative importance of a downward O⁺ flux and an upward ion drift in maintaining the F-region under SAR-arc conditions. It was found that the upward drift caused a marked increase in the NO⁺/O⁺ transition altitude as high as 460 km at night. However, for typical drift speeds up to 50 m sec^?1 the peak electron density was lower than experimental observations. The effect of a large, short-duration perpendicular electric field on the SAR-arc ion and electron density profiles was found to be small. In all cases considered the magnitude of the enhanced NO⁺ density as a result of vibrationally excited N₂ molecules was sufficient to prevent the electron density within the night-time SAR-arc from becoming vanishingly small.     

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.     

Excitation of O(1S) and emission of 5577 Å radiation in aurora

The results of recent laboratory experiments suggest that the reaction N⁺ + O₂ → NO⁺ + O(¹S) is the principal source of O(¹S) in aurora. A negligible time delay between auroral ionization and O(¹S) production is associated with this indirect process, which is a necessary condition for a viable mechanism. The $\text{5577}\text{A}\text{?}\text{3914}\text{A}\text{?}$ volume emission rate ratio associated with this production source remains constant with altitude. The problems encountered by the currently accepted source of O(¹S), the reaction of N₂(A³Σ) molecules with atomic oxygen are explored, and the contributions of this and other reactions to the auroral green line emission are reevaluated.     

The dissociative recombination of N2+ (v = 0, 1) as a source of metastable atoms in planetary atmospheres

The yield of metastable nitrogen atoms in dissociative recombination of N₂⁺ (v = 0, 1)ions has been tudied for different experimental conditions. In a first experiment, the branching ratio for N(²D) production was directly measured as being higher than 1.85; for N₂⁺ (v = 0) this implies that ²D + ²D is the main reaction channel; for N₂⁺ (v = 1) a minor channel could be ²P + ²D, ²P being then quenched toward ²D by electrons. In a second experiment, at higher electron densities, the influence of superelastic collisions was studied; a steady state analysis yields the quenching rate coefficient k₄, of ²D towards ⁴S equal to 2.4 × 10^?10 cm³ s^?1for T_e = 3900 K and shows that ²D + ²D is always the major channel of the reaction for N₂⁺ (v = 1), ²D + ²P being a minor channel. All these results are in good agreement with thermospheric models but imply that N₂⁺ dissociative recombination is a less important source for nitrogen escape of Mars.     

Isotope identification in NO as a chemical tracer in the middle atmosphere

The nitrogen isotope ratio of middle atmosphere nitrogen oxide is predicted as a function of altitude. Nitrogen oxides originate photochemically either from stratospheric nitrous oxide reacting with O(¹D) or in the mesosphere and thermosphere from direct dissociation of N₂ and ionization-initiated reactions involving O₂ and N₂. During its formation process, N₂O acquires a nitrogen isotopic composition of N isotopes different than N₂. Photodissociation within the stratosphere also modifies the proportion of isotopes. Reaction of stratospheric NO with O₃ produces NO₂, which when photodissociated yields NO depleted in ¹⁵N relative to NO₂ in laboratory air. The value of δ¹⁵NO in the stratosphere is −100‰. In the altitude region between 50 and 65 km, NO is transformed into NO₂ and then returned to NO by reaction of NO₂ with O and by NO₂ photodissociation. These reactions determine the isotopic makeup of NO. Above 65 km, nitric oxide is produced by local ionization processes and gas phase photochemical reactions involving N₂ and excited O₂. These processes determine the isotopic composition of NO in the upper mesosphere and thermosphere. Here δ¹⁵NO is 0‰. Air transported into the mesosphere above 65 km will reflect the NO isotopic values of the region below, while mesospheric NO transported below 65 km will not be distinguishable from NO originating in the stratosphere.     

Auroral recombination of N and O: A possible source for emission in the γ and δ bands of NO

Radiative recombination of N and O provides a significant source for auroral emission in the γ and δ bands of NO with selective population of vibrational levels in the A²Σ⁺ and C²Π states. This mechanism may account for emissions detected near 2150 Å. Models are derived for the auroral ionosphere and include estimates for the concentrations of N and NO. The concentration of NO is estimated to have a value of about 10⁸ cm^?1 near 140 km in an IBC III aurora. The corresponding density for N is about 5 × 10⁷cm^?3 and the concentration ratio $\text{NO}{}^{\mathrm{+}}\text{O}{}_2{}^{\mathrm{+}}$ has a value of about 5.5.     

EUV resonance fluorescence of the c′4→X (0,v″) and b′→X (1,v″) transitions of N2

Extreme ultraviolet (EUV) resonance fluorescence of the (0,v″) bands of the c′₄¹Σ_u⁺→X¹Σ_g⁺ and the (1,v″) bands of the b′ ¹Σ_u⁺→X¹Σ_g⁺ transitions of N₂ has been observed by photon excitation of N₂ in the vicinity of 95.8 nm. The integrated fluorescence intensities of the c′₄→X (0,v″) emission become saturated at N₂ pressures higher than ∼0.16 mTorr. The emission features in the spectral region between 105 and 130 nm become progressively significant as the N₂ pressure is increased. The (1,v″) progression for v″ up to 11 of the b′→X transition and two progressions of the Lyman-Birge-Hopfield (LBH) system have been identified. The multiple scattering processes apparently cause significant reduction in the c′₄→X (0,0) emission rates. The present results may be useful in the explanation of the weak c′₄→X (0,0) fluorescence as well as the significant c′₄→X (0,v″) features in the dayglow of the Earth observed by the Far Ultraviolet Spectroscopic Explorer.     

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.     

Laboratory measurements of the association rate coefficients of NO+, O+2, N+, and N+2 ions with N2 and CO2 at temperatures between 100 k and 400 k

Rate coefficients for the association reactions of NO⁺ ions with N₂ and CO₂, O₂⁺ with N₂, and N⁺ and N₂⁺ with N₂ have been determined as a function of gas temperature in a laboratory experiment employing a variable-temperature drift-tube apparatus. The measured rate coefficients were fitted to power laws of the form $\text{k = C}\text{(}\text{T}\text{300}\text{)}{}^{\mathrm{x}}$ where the exponents x ranged from 2.2 to 4.3. The strong temperature dependence observed in the case of the reaction of NO⁺ with N₂ (x = 4.3) supports the thesis by Arnold et al. (1979) that the temperature variability of D-region ion densities is a result of this reaction step in the ion clustering sequence.     

Impact processing of nitrogen on early Mars

An intense impact flux upon a planet having a CO₂ + N₂ atmosphere, such as Mars, provides energy to synthesize nitric oxide, NO, which is likely converted into nitrate minerals. The same impact flux can decompose nitrate minerals if present in the crust. We build a numerical model to study the effects of early impact processes on the evolution of nitrogen in a dominantly CO₂ atmosphere. We model the period of intense post-accretionary bombardment, the roughly 500 Myr period after crustal stabilization that locks in previously accreted volatiles. A best-guess, “fiducial” set of parameters is chosen, with a fixed “veneer” of post-accretionary impactors (δR=950 m thick), assumed to contain carbon at 1 wt% (fg=0.01), with a molar C/N ratio of 18, an initial atmospheric pressure of 1 bar (with CO₂/N₂ = 36), and a power law impactor mass distribution slope b=0.75. This model produces a nitrate reservoir RNO₃?0.5×¹⁰¹⁹ moles, equivalent to ∼30 mbars of N₂, during the intense impact phase. Starting with 1 bar, the atmosphere grows to 2.75 bars. Results of models with variations of parameter values show that RNO₃ responds sluggishly to changes in parameter values. To significantly limit the size of this reservoir, one is required to limit the initial total atmospheric pressure be less than about 0.5 bars, and the impactor volatile content fg to be less than 0.003. The value of fg substantially determines whether the atmosphere grows or not; when fg=0.01, the atmosphere gains about 1.7 bars, while for fg=0.003, the atmosphere gains less than 200 mbars, and for fg=0.001, it loses about 400 mbars. Impact erosion is a minor sink of N, constituting generally less than 10% of the total supply. The loss of impactor volatile plumes can take almost 50% of incoming N and C under fiducial parameters, when atmospheric pressures are low. This nitrogen does not significantly interact with Mars, and hence is not properly delivered. When the initial N is greater than the delivered N, most of the nitrogen ends up as nitrates; when delivered N is larger, most nitrogen ends up in the atmosphere. The reason for this dichotomy seems to be that initial nitrogen is present during the whole bombardment, while delivered N, on average, only experiences half the bombardment. The operating caveat here is that the above results are all conditioned on the assumption that impact processes dominate this period of Mars atmospheric evolution.     

The evolution and variability of atmospheric ozone over geological time

The rise of atmospheric O₃ as a function of the evolution of O₂ has been investigated using a one-dimensional steady-state photochemical model based on the chemistry and photochemistry of O_x(O₃, O, O(¹D)), N₂O, NO_x(NO, NO₂, HNO₃), H₂O, and HO_x(H, OH, HO₂, H₂O₂) including the effect of vertical eddy transport on the species distribution. The total O₃ column density was found to maximize for an O₂ level of 10^?1 present atmospheric level (PAL) and exceeded the present total O₃ column by about 40%. For that level of O₂, surface and tropospheric O₃ densities exceeded those of the present atmosphere by about an order of magnitude. Surface and tropospheric OH densities of the paleoatmosphere exceeded those of the present atmosphere by orders of magnitude. We also found that in the O₂-deficient paleoatmosphere, N₂O (even at present atmospheric levels) produces much less NO_x than it does in the present atmosphere.     

Ion composition in the E- and lower F- region above kiruna during sunset and sunrise

A magnetic type mass spectrometer has been flown on two ESRO sounding rockets from ESRANGE (Kiruna 68°N) on February 25 and 26, 1970. The first launch was at sunset (16:33 UT) and the second the next morning, during sunrise (04:47 UT). For both flights the solar zenith angle was approximately 98°. The instrument was measuring simultaneously the neutral gas and positive ion composition and the total ion density. In this paper the results of the ion composition measurements are presented. For both flights the main ion constituents measured between approximately 110–220 km were O⁺, NO⁺ and O₂⁺. Only at sunset were N⁺ and N₂⁺ detected above 200 km. In spite of the identical solar UV-radiation, pronounced sunset/sunrise variations in the positive ion composition were found. The total ion densities at sunrise were between 5×10³ and 5 × 10⁴ ions cm^?3 and therefore too high to be explained without a night-time ionization by precipitated particles. At sunrise the NO⁺ and O₂⁺ profiles show a correlated wavelike structure with three pronounced almost equally spaced layers in the E-region. Only the highest layer is present in the O⁺ profile. Locally enhanced field aligned ionization originated by particle precipitation and an E × B instability are the most likely source for this structure. In the E- and lower F-regions the $\text{NO}{}^{\mathrm{+}}\text{O}{}_2{}^{\mathrm{+}}$ ration increased overnight from values around 7 at sunset to 15 at sunrise, correlated with an increase of the local magnetic activity index K from 0⁺ to 2°. This could be explained if the NO density and magnetic activity are correlated.     

Winter anomalous D-region over Sardinia (40°N)

A simplified D-region model consisting of O₂⁺, NO⁺ and their respective cluster ions grouped as Z_o2⁺ and Z_NO⁺ is used to reproduce the available rocket data on positive ion relative composition and effective clustering rates for the height range 70–90 km. The results of this analysis for a winter anomalous day (Sardinia, 40°N) are in good agreement with the presently known ideas on NO densities, O₂⁺ production rates, mesospheric temperature, negative ion to electron density ratio and effective loss coefficient for electrons. Mesospheric nitric oxide density and temperature profiles from this study are in excellent agreement with the findings of Zbinden et al. (1975) and Hidalgo (1977) for the anomalous day at Sardinia.     

The production of water-cluster positive ions in the quiet daytime D region

In the quiet daytime D region, the primary positive-ion species is thought to be NO⁺, produced by solar Lyman-alpha ionization of NO. Below the altitude of the mesopause, however, the dominant ambient species observed are water-cluster ions of the general type H⁺(H₂O)_n. No satisfactory reaction scheme for producing these cluster ions from NO⁺ has yet been proposed. Following earlier suggestions, a model calculation has been carried out in which successive hydrations of NO⁺ take place through clustering with N₂ and CO₂, followed by “switching” reactions with H₂O. The third hydrate of NO⁺ is then converted into the water-cluster species H⁺(H₂O)₃, and the other water-cluster species are produced by successive clustering and thermal breakup reactions. Many of the reactions involved have not been measured in the laboratory, but reasonable estimates of their rates can be made on the basis of existing measurements of other species. Since both temperature and water-vapor content are of major importance in the model, calculations were carried out for two temperature profiles and two water-vapor profiles. It is shown that the results are in reasonably good agreement with observations as far as the water-cluster species are concerned. Under low-temperature conditions, the model predicts relatively large concentrations of various clusters of NO⁺, in agreement with some observations but in disagreement with others. The importance of sampling breakup of these weakly bound clusters, and their relevance to the free electron concentrations are discussed.     

Ground-based observations of O2 (b1Σ+g−X3Σ−g) atmospheric bands in high latitude auroras

Analysis of observed spectrograms is based on comparison with synthetic spectra. The O₂(b¹Σ⁺_g?X³Σ^?_g Atm. (1,1) band in high latitude auroras observed from the ground is found to be the strongest in the Δv = 0 sequence. It is enhanced with altitude relative to the N₂ 1P(2, 0)and N⁺₂ M(2,0) bands, but the O₂ Atm. (2, 2) band has an unexpected low intensity. The range of rotational temperatures of the O₂ Atm. bands varies from approx. 200 to above 500 K which indicates that the altitude of the centroid of the emission region varies from about 100 km to the F-region. The highest temperature is found in the midday aurora associated with the magnetospheric cusp. Conspicuous relative variations between the intensities of N₂ and O₂ spectra are documented, but a satisfactory explanation of the variety is not given. Deviations of the observed O₂ Atm. band intensities from the vibrational intensity distribution predicted by Franck-Condor factors indicate that the excitation of the O₂ Atm. bands in aurora is not mainly due to particle impact on O₂, and the contribution due to energy transfer from hot O(¹D) atoms has to be found in future research.