Auroral implications of recent measurements on O(1S) and O(1S) formation in the reaction of N+ with O2

Recent flowing afterglow measurements have shown that the reaction of N⁺ with O₂ produces 70 ± 30% of the oxygen atom product as $\text{O}\text{(}{}^1\text{D}\text{)}$ and < 0.1% as $\text{O}\text{(}{}^1\text{S}\text{)}$. These results indicate that this reaction does not contribute to the auroral green line emission (5577 Å), but can account for ～10% of the observed red line (6300 Å) auroral emission.     

Thermospheric neutral composition from auroral ion ratios

For nighttime auroras, we find that positive ion ratios are only a function of the neutral atmospheric composition and of the pertinent ionic processes if the ions are depleted mainly by ion-molecule reactions. Ionic ratios calculated for $\text{[}\text{N}{}^{\mathrm{+}}\text{]}\text{[}\text{N}{}_2{}^{\mathrm{+}}\text{]}$ using the 1976 U.S. Standard Atmosphere and laboratory rate coefficients (with one exception) rise smoothly with altitude: 0.1 (120 km), 0.3 (140 km), 0.6 (160 km), 1.0 (180 km) and 1.5 (200 km). These values compare favorably with experimental ratios from three different auroral experiments. The exception refers to our use of a larger rate coefficient for N₂⁺ + O → NO⁺ + N than found in the laboratory. We also determine an $\text{[}\text{N}{}_2{}^{\mathrm{+}}\text{]}\text{[}\text{O}{}^{\mathrm{+}}\text{]}$ ratio with altitude: 0.36 (120 km), 0.078 (140 km), 0.030 (160 km), 0.014 (180 km) and 0.0075 (200 km). These values compare favorably with results from the same three auroral experiments. However, the match with a fourth auroral experiment is poor. Except for this last case, we conclude that the neutral composition at auroral latitudes in late winter is similar to the U.S. Standard for the altitudes examined.     

Quantal calculation of the lifetime of N+(5S) and the λ2145Å auroral mystery feature

The calculated radiative lifetime of the metastable ion is 6.4 × 10^?3s. Used in conjunction with the results of measurements by Erdman, Espy and Zipf this sets 1.3 × 10^?18 cm² as the upper limit to the cross section for the formation of $\text{N}{}^{\mathrm{+}}\text{(}{}^5\text{S}\text{)}$ in e - N₂ collisions at 100eV which leaves the possibility that the process is responsible for the $\text{λ2145}\text{A}\text{?}$ feature in auroras only just open. The cross section for the formation of $\text{N}{}^{\mathrm{+}}\text{(}{}^5\text{S}\text{)}$ in e — N collisions is large. However for this process to lead to the observed intensity of $\text{λ2145}\text{A}\text{?}$ relative to $\text{λ3914}\text{A}\text{?}$ the N:N₂ abundance ratio would have to be as high as 1.6 × 10^?2.     

Quenching of O+(2D) by electrons in the thermosphere

A major loss process for the metastable species, O⁺(²D), in the thermosphere is quenching by electrons

$\text{O}{}^{\mathrm{+}}\text{(}{}^2\text{D) + e → O}{}^{\mathrm{+}}\text{(}{}^4\text{S) + e}$

.To date no laboratory measurement exists for the rate coefficient of this reaction. Thermospheric models involving this process have thus depended on a theoretically calculated value for the rate coefficient and its variation with electron temperature. Earlier studies of the O⁺(²D) ion based on the Atmosphere Explorer data gathered near solar minimum, could not quantify this process. However, Atmosphere Explorer measurements made during 1978 exhibit electron densities that are significantly enhanced over those occurring in 1974, due to the large increases that have occurred in the solar extreme ultraviolet flux. Under such conditions, for altitudes ? 280 km, the electron quenching process becomes the major loss mechanism for O⁺(²D), and the chemistry of the N⁺₂ ion, from which the O⁺(²D) density is deduced, simplifies to well determined processes. We are thus able to use the in situ satellite measurements made during 1978 to derive the electron quenching rate coefficient. The results confirm the absolute magnitude of the theoretical calculation of the rate coefficient, given by the analytical expression k(T_e) = 7.8 × 10^?8 (T_e/300)^?0.5cm³s^?1. There is an indication of a stronger temperature dependence, but the agreement is within the error of measurement.     

Aeronomical determination of the efficiency of O1D) production by dissociative recombination of O2+

Simultaneous measurements of the 6300 Å airglow intensity, the electron density profile, and F-region ion temperatures and vertical ion velocities taken at the Arecibo Observatory in March 1971 are utilized in the height integrated continuity equation to extract the number of photons'of 6300 Å emitted per recombination. After accounting for quenching of $\text{O}\text{(}{}^1\text{D}\text{)}$ and the electrons lost via NO⁺ recombination, the efficiency of $\text{O}\text{(}{}^1\text{D}\text{)}$ production by the dissociative recombination of O₂⁺ is determined to be 0.6 ± 0.2 including cascading from the $\text{O}\text{(}{}^1\text{S}\text{)}$ state. The uncertainty includes both random measurement errors and estimates of possible systematic errors.     

Associative ionization of N(2D) and O

Recent laboratory measurements have shown that N(²P) atoms, and thus probably hot N(²D) atoms, will recombine with atomic oxygen via an associative ionization process at the gas kinetic rate. While the reaction is endothermic, it has been suggested that this has interesting implications for the upper atmosphere in that N(²D) atoms in the tail of the velocity distribution could provide an additional source of NO⁺ through the reverse of the dissociative recombination reaction

$\text{NO}{}^{\mathrm{+}}\text{+ e ?}\text{N}\text{(}{}^2\text{D}\text{) +}\text{O}$

. It has also been suggested that this process might account for the difference between a laboratory determination of the rate coefficient and that determined from the Atmospheric Explorer Satellite data. In this paper we investigate further the likelihood of the associative ionization of N(²D) and O playing a significant role in the normal ionosphere, in the light of several recent relevant studies. We conclude that the associative ionization process is not an important factor and that a more probable cause for disagreements in the various determinations of the recombination coefficient, is the difference in excited states of the ions in the various experiments.     

The chemistry of metastable species in the Venusian ionosphere

Reactions of metastable species are important in determining the densities of minor ions in the Venusian ionosphere. Calculations are carried out in which the coupled continuity and momentum equations are solved for twelve ions and four neutral species in the dayside ionosphere, including $\text{O}{}^{\mathrm{+}}\text{(}{}^2\text{D),}\text{O}{}^{\mathrm{+}}\text{(}{}^2\text{P),}\text{N}\text{(}{}^2\text{D),}\text{and N}\text{(}{}^2\text{P)}$. Altitude profiles of these metastable species are presented. Their reactions are shown to be a significant source of several minor ions, especially N₂⁺, CO⁺, and N⁺. The discrepancies which existed between model and measured densities of these ions are resolved.     

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.     

A self-consistent evaluation of the rate constants for the production of the OI 6300 Å airglow

The quenching rate k_N2 of $\text{O(}{}^1\text{D)}$ by N₂ and the specific recombination rate α_1D of O₂⁺ leading to $\text{O(}{}^1\text{D)}$ are re-examined in light of available laboratory and satellite data. Use of recent experimental values for the $\text{O(}{}^1\text{D)}$ transition probabilities in a re-analysis of AE-C satellite 6300 Å airglow data results in a value for k_N2 of 2.3 × 10^?11 cm³s^?1 at thermospheric temperatures, in excellent agreement with the laboratory measurements. This implies a value of J_O2 = 1.5 × 10^?6s^?1 for the O₂ photodissociation rate in the Schumann-Runge continuum. The specific recombination coefficient α_1D = 2.1 × 10^?7cm³s^?1 is also in agreement with the laboratory value. Implications for the suggested $\text{N}\text{(}{}^2\text{D) + O}{}_2\text{→ O(}{}^1\text{D) + NO}$ reaction are discussed.     

The problem of auroral NO+ concentration and the intensity of 1·27μ bands of O2

The problem of the theoretical computation of the emission intensities and ion composition in a weak aurora which has been preceded by a stronger event is examined. For this purpose a model auroral precipitation consisting of biexponential primaries is considered. The softer of the two components is brighter, and begins to decay after remaining steady for ten to fifteen minutes. The other, harder component starts to build up at that instant. Our results suggest that at least a part of the high $\text{n(}\text{NO}{}^{\mathrm{+}}\text{)}\text{n(}\text{O}{}_2{}^{\mathrm{+}}\text{)}\text{or}\text{I}\text{(1·27 μ)}\text{I}\text{(3914}\text{A}\text{?}\text{)}$ ratios could be attributed to the retention, by the atmosphere, of the memory of previous auroral precipitations. Thus, the serious energy paradox in the context of 1·27 μ intensity need not arise, and, in the context of the large NO⁺ density, it may perhaps be unnecessary to invoke any major conversion of O₂ to NO thus avoiding the associated energy problem.     

Ion-ion recombination rates in the earth's atmosphere

The temperature dependence of the binary recombination coefficient, α₂, for the reaction NO⁺+NO₂^? → products has been obtained over the range 185–530 K. It is found that the corresponding mean cross section $\text{σ}$ is described by the power law $\text{σ}\text{? A · T}{}^{\mathrm{?0.9}}$, and that α₂ ? B · T^?0.4. Data has also been obtained for two cluster ion recombination reactions which indicate that their recombination cross sections are only about 40% larger than for the parent ions at a given temperature, the cross sections for these reactions also apparently increasing with decreasing temperature. In the light of this data and by considering the most probable positive and negative ions existing at various altitudes up to 90km in the atmosphere, the most appropriate ionic recombination coefficients in various altitude ranges are deduced. Thus, between 30 and 90 km, where the recombination process is two-body, the coefficient varies over the narrow range 5–9 × 10^?8 cm³s^?1, while below 30 km the process is predominantly three-body with an effective two-body rate increasing rapidly to a maximum value ≈3 × 10^?6 cm³s^?1 in the troposphere, these deductions being based on published laboratory determinations of three-body recombination coefficients.     

The O(1S) quantum yield from O2+ dissociative recombination

Recent laboratory studies show that the $\text{O}\text{(}{}^1\text{S}\text{)}$ quantum yield, $\text{f}\text{(}{}^1\text{S}\text{)}$, from O₂⁺ dissociative recombination varies considerably with the degree r of vibrational excitation. However, the suggestion that the high values for $\text{f}\text{(}{}^1\text{S}\text{)}$ deduced from airglow and auroral observations can be explained by invoking vibrational excitation, creates a number of problems. Firstly, the rapid vibrational deactivation of O₂⁺ ions by collisions with O atoms will keep r too low to account for the magnitude of $\text{f}\text{(}{}^1\text{S}\text{)}$; secondly, r varies considerably from one atmospheric source to another but its relative values (which should be reliable) do not co-vary with those of $\text{f}\text{(}{}^1\text{S}\text{)}$; thirdly, because r increases markedly above the peak of the $\text{X5577}\text{A}\text{?}$ dissociative recombination layer, the fits which theorists have obtained to the observed volume emission rate profiles would have to be regarded as fortuitious. It is tentatively suggested that $\text{f}\text{(}{}^1\text{S}\text{)}$ is higher in the airglow and aurora than in the laboratory plasma studied by Zipf (1980) because of the electron temperature dependence of the $\text{O}\text{(}{}^1\text{S}\text{)}$ specific recombination coefficient for O₂⁺(v^' ? 3) ions.The repulsive ${}^1\text{Σ}{}_{\mathrm{<mtext>u</mtext>}}\text{[}{}^1\text{D}\text{+}{}^1\text{s}\text{]}$ state of O₂ does not provide a suitable channel for the dissociative recombination. A possible alternative is the bound ${}^3\text{Π}{}_{\mathrm{<mtext>u</mtext>}}\text{[}{}^5\text{S}\text{+}{}^3\text{s}\text{]}$ state with predissociation to the repulsive ${}^3\text{Π}{}_{\mathrm{<mtext>u</mtext>}}\text{[}{}^3\text{P}\text{+}{}^1\text{s}\text{]}$ state.     

On the simultaneous ionization-excitation of the OII(λ834 Å) resonance transition by electron impact on atomic oxygen

Laboratory cross-section data on the excitation of the OII(2s 2p⁴⁴P → 2s² 2p³⁴S; λ834 Å) resonance transition and on the production of O⁺ and O²⁺ ions by electron impact on atomic oxygen are used to show that the ratio $\text{σ(λ834}\text{A}\text{?}\text{)}\text{σ(O}{}^{\mathrm{+}}\text{+ O}{}^{\mathrm{2+}}\text{)}$ is nearly constant for incident electron energies > 50 eV. Under auroral conditions, the total electron-ion pair production rate from electron impact on O can be inferred from λ834 Å volume emission rate measurements using the result that $\text{η(O}{}^{\mathrm{+}}\text{+ O}{}^{\mathrm{2+}}\text{)}\text{\$}\text{?}\text{8.4η(λ834}\text{A}\text{?}\text{)}$. These findings, along with earlier work on the simultaneous ionization-excitation of the 1 Neg (0,0) band of N₂⁺ and the 1 Neg (1, 0) band of O⁺₂, allow the specific ionization rates for the principal atmospheric constituents (O⁺, O⁺₂, N⁺₂), for the multiply-ionized species (O²⁺, O²⁺₂, N²⁺₂), and for the dissociatively produced atomic ions to be inferred in aurora from remote satellite observations.     

Airglow from the inner comas of comets

The intensities of radiation from the inner comas of comets which are composed primarily of water and carbon monoxide have been calculated. Only “airglow” emissions initiated by the absorption of extreme ultraviolet radiation have been considered. The photoionizations of H₂O, CO, CO₂, and N₂ are the most important emission sources, although photoelectron excitation is also considered. Among the emission features for which intensities were calculated are H₂O⁺ ($\text{A}\text{?}{}^2\text{A}{}_{\mathrm{1?}}\text{X}\text{?}{}^2\text{B}{}_1$), CO⁺ (first negative), CO (fourth positive), CO (Cameron), CO₂⁺ ($\text{B}\text{?}{}^2\text{?}{}_{\mathrm{u}}\text{?}\text{X}\text{?}{}^2\text{II}{}_{\mathrm{g}}$), N₂ (Vegard-Kaplan), N₂⁺ (first negative), and OI (1304 Å). In the inner coma (collision region) these airglow mechanisms are shown to be possible competitors with the usually assumed resonance scattering and flourescence excitation mechanisms which are appropriate for the outer coma and tail.     

Charge exchange of metastable D oxygen ions with N2 in the thermosphere

Measurements of N₂⁺ and supporting data made on the Atmosphere Explorer-C satellite in the ionosphere are used to study the charge exchange process

$\text{O}{}^{\mathrm{+}}\text{(}{}^2\text{D}\text{)+}\text{N}{}_2\text{→}\text{k}\text{N}{}^{\mathrm{+}}{}_2\text{+}\text{O}$

The equality k = (5 ± 1.7) × 10^?10cm³s^?1. This value lies close to the lower limit of experimental uncertainty of the rate coefficient determined in the laboratory. We have also investigated atomic oxygen quenching of O⁺(²D) and find that the rate coefficient is 2 × 10^?11 cm³s^?1 to within approximately a factor of two.     

The excitation of atomic oxygen to the O(1S) level by energy transfer from N2(A3∑u+) molecules in aurora

The part that the energy transfer reaction $\text{N}{}_2\text{(A}{}^3\text{∑}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{) + O(}{}^3\text{P) → N}{}_2\text{(X}{}^1\text{∑}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{) + O(}{}^1\text{S)}$ plays in the excitation of the auroral green line has been investigated. The contribution is estimated to be 40 per cent in this case, containing pulsating aurora in class IBC 1. Due to greater quenching of the A³∑_u⁺ state, the centroid of the VK emission is displaced 10 km upwards of the green line height, which is centred at 110 km.     

Reaction of protons with methane in the Jovian ionosphere

Laboratory data shows that the reaction of protons with methane proceeds at thermal ion energies to give both CH₃⁺ and CH₄⁺ ions in the ratio $\text{CH}{}_3{}^{\mathrm{+}}\text{CH}{}_4{}^{\mathrm{+}}\text{= 1.5 ± 0.3}$. The overall rate constant for the reaction is 3.8 ± 0.3 × 10^?9 cm³/sec. This reaction may lead to the formation of hydrocarbon ions in the lower ionosphere of Jupiter, and the significance of this process for formation of hydrocarbons and HCN in the atmosphere of Jupiter is discussed.     

Cross-section for the dissociative photoionization of hydrogen by 584 Å radiation: The formation of protons in the Jovian ionosphere

The cross-section for dissociative photoionization of hydrogen by 584 Å radiation has been measured, yielding a value of 5 × 10^?20 cm². The process can be explained as a transition from the $\text{X}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ ground state to a continuum level of the $\text{X}{}^2\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ ionized state of H₂ The branching ratio for proton (H⁺) vs molecular ion (H₂⁺) production at this energy is 8 × 10^?3. This process is quite likely an important source of protons in the Jovian ionosphere near altitudes where peak ionization rates are found.     

Observations and interpretation of spectra and rapid time variations of type-B aurora

Observations of type-B red and normal aurora were made with a high-speed multichannel photometer and a digital grating spectrometer. The ratio $\text{I}\text{(}\text{O}{}_2{}^{\mathrm{+}}\text{1N; 2, 0 + 3, 1)}\text{I}\text{(}\text{N}{}_2{}^{\mathrm{+}}\text{1N; 0, 3)}$ measured in the 5200–5300 Å region with the spectrometer was found to increase by about 16% from normal to type-B aurora. This small change is difficult to reconcile with a height below 90 km for the red border. In the type-B aurora, λ 5577 was weakened by a factor between 1.9 and 3.8 while the ratio $\text{I}\text{(}\text{N}{}_2\text{1P; 5, 2)}\text{I}\text{(}\text{N}{}_2{}^{\mathrm{+}}\text{1N)}$ was enhanced less than 20%. Rapid intensity variations in the type-B lower border were observed in the λ 5577 and other channels of the photometer. A revised time dependent auroral excitation-ion chemistry model is used in an attempt to reproduce the observations. The observed weakening of λ 5577 could be produced at heights equal to or less than 100 km while the short observed time lag of λ 5577 on the N₂⁺ 1N emission is easier to explain at 100 km than at 80 km. It is concluded that some type-B lower borders may occur near 100 km although it is recognized that there is good evidence rare deep crimson lower borders lie at 80 km or below. The mechanism for the excitation of O(¹S) is considered in the light of these results. None of the mechanisms examined is satisfactory on the basis of currently accepted atmospheric models and quenching rate coefficients.