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 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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Cosmic ray synthesis of organic molecules in Titan's atmosphere

We have studied the possible synthesis of organic molecules by the absorption of galactic cosmic rays in an N₂CH₄H₂ Titan model atmosphere. The cosmic-ray-induced ionization results in peak electron densities of 2 × 10³ cm^?3, with NH₄⁺, C₃H₉⁺, and C₄H₉⁺ being among the important positive ions. Details of the ion and neutral chemistry relevant to the production of organic molecules are discussed. The potential importance of $\text{N}\text{(}{}^2\text{D)}$ reactions with CH₄ and H₂ is also demonstrated. Although the integrated production rate of organic matter due to the absorption of the cosmic ray cascade is much less than that by solar ultraviolet radiation, the production of nitrogen-bearing organic molecules by cosmic rays may be greater.     

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.     

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.     

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.     

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.     

Collisional vibrational quenching of O2+(v) and other molecular ions in planetary atmospheres

New experimental techniques have yielded several thermal energy vibrational quenching rate constants for O₂⁺(v). Rates for quenching of O₂⁺(v = 1) by O₂, N₂, Ar, CO₂, H₂, and CH₄ are 3(?10), 2(?12), 1(?12), 1(?10), 2.5(?12), and 6(?10) cm³s^?1 at 300 K. The quenching is somewhat faster for O₂⁺(v = 2). The triatomic ions CO₂⁺, NO₂⁺, N₂O⁺, SO₂⁺, and H₂O⁺ are all vibrationally deexcited with an efficiency greater than 10^?3 in Ar or Ne collisions. A theoretical rationalization of the experimental results leads to the prediction that vibrational quenching in planetary atmospheres will generally be efficient, k > 1(?12) cm³s^?1 for almost all ion and neutral gas pairs.     

Consistency tests of cosmogonic theories from models of Uranus and Neptune

The planetary ratios of ice to rock $\text{(}\text{I}\text{R}\text{)}$ abundances expected in Uranus and Neptune are derived on the basis of several cosmogonic theories. For both Uranus and Neptune the value of $\text{I}\text{R}$ lies between about 1.0 and 3.6. This value is difficult to reconcile with a scenario in which N and C are accreted primarily in the form of N₂ and CO. It is consistent with some versions of both giant protoplanet theories and equilibrium accretion theories.     

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.     

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.