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.     

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.     

Fluorescence efficiencies of electrons in molecular nitrogen and oxygen gases

Fluorescence efficiencies of electrons in a large number of bands of the N₂ First Positive and O₂⁺ First Negative groups lying in the 4900–10,500 Å wavelength range have been investigated theoretically. The variation of transition moment with internuclear distance is taken into consideration. For the First Positive group of N₂ the calculations are carried out at very low pressure as well as at 600 Torr. In general the present values are higher than the experimental values but in most of the cases fair agreement has been obtained. For the O₂⁺ First Negative group no direct experimental data is available. However, the present ratio of the total efficiency in the O₂⁺ First Negative group to the N₂⁺ First Negative group is found to be in good agreement with the experimental intensity ratio.     

Errors in calculated values of electron temperatures in H II regions

This paper considers the classical method to determine the electron temperatures t _3,O, t _2,O and t _2,N from forbidden lines of the ions O⁺⁺, O⁺, and N⁺, and investigates the influence of uncertainties in atomic data on the accuracy of the determined electron temperatures. The uncertainties in atomic data (the Einstein coefficients for spontaneous transitions and electron ionization cross-sections) are estimated as discrepancies between the values computed by various authors. The error in the electron temperature caused by uncertainties in the atomic data is found to increase with the growth in the electron temperature. At a temperature 10000 K, the errors in the electron temperatures t _3,O, t _2,N, and t _2,O do not exceed 1, 3, and 7%, respectively.     

A study of the excitation and radiative decay of the 3s′ 3D0 and 3d 3D0 levels of atomic oxygen

The absolute cross-sections for the excitation of the 989 Å, 1027 Å, 7990 Å, 8446 Å, 1.1287 μm and 1.3164 μm multiplets of atomic oxygen by electron impact dissociation of O₂ are reported. The radiative branching ratios for these transitions are calculated from these results and compared with the NBS compilation of Wiese et al. (1966) and the recent theoretical calculations of Pradhan and Saraph (1977). The cascade models of O⁺ radiative recombination and of electron-impact excitation of the OI(³S) state in the terrestrial airglow are discussed in the light of the laboratory measurements, and the effects of the resonant absorption of components of the λ 989 Å and λ. 1027 Å multiplets by the Birge-Hopfield band system of N₂ are investigated. This process is shown to depend sensitively on the N₂ vibrational temperature and to cause characteristic changes in the OI e.u.v. emission spectrum in auroras and in the sunlit F-region at high exospheric temperatures. It is also suggested that the λ 1027 Å radiation observed in auroral spectra is actually due to molecular nitrogen band emission that has been enhanced by entrapment effects and not to the excitation of the 2p ³P-3d ³D⁰ transition of atomic oxygen as believed previously.     

The role of ion-molecule reactions in the conversion of N2O5 to HNO3 in the stratosphere

We have investigated the role of several ion-molecule reactions in the conversion of N₂O₅ to HNO₃. In the proposed conversion, an N₂O₅ molecule would react with an H₂O molecule clustered to an inert ion to produce two HNO₃ molecules. Subsequent clustering of an H₂O molecule to the inert ion would make the reaction catalytic. If such an ion-catalysed conversion of N₂O₅ to HNO₃ occurs, it would probably play a role in the stratospheric chemistry at high latitudes in winter. In this paper we present reaction rate constant measurements made in a flowing afterglow apparatus for hydrated H₃O⁺, H⁺(CH₃CN)_m (m = 1, 2, 3), and several negative ions reacting with N₂O₅. Slow rate constants were found for these ions for hydration levels that are predominant in the stratosphere. With the known stratospheric ion density, these slow rate constants preclude significant N₂O₅ conversion by ion-molecule reactions.     

Photochemistry of nitrogen in the Martian atmosphere

Models are developed for the photochemistry of a CO₂H₂ON₂ atmosphere on Mars and estimates are given for the concentrations of N, NO, NO₂, NO₃, N₂O₅, HNO₂, HNO₃, and N₂O as a function of altitude. Nitric oxide is the most abundant form of odd nitrogen, present with a mixing ratio relative to CO₂ of order 10^?8. Deposition rates for nitrite and nitrate minerals could be as large as 3× 10⁵ N equivalent atoms cm^?2 sec^?1 under present conditions and may have been higher in the past.     

Electronic Sputtering Analysis of Astrophysical Ices

Experimental results on fast ion collision with icy surfaces having astrophysical interest are presented. ²⁵²Cf fission fragments projectiles were used to induce ejection of ionized material from H₂O, CO₂, CO, NH₃, N₂, O₂ and Ar ices; the secondary ions were identified by time-of-flight mass spectrometry. It is observed that all the bombarded frozen gas targets emit cluster ions which have the structure X_nR^±, where X is the neutral ice molecule and R^± is either an atomic or a molecular ion. The shape of the positive or negative ion mass spectra is characterized by a decreasing yield as the emitted ion mass increases and is generally described by the sum of two exponential functions. The positive ion water ice spectrum is dominated by the series (H₂O)_nH₃O⁺ and the negative ion spectrum by the series (H₂O)_nOH⁻ and (H₂O)_nO⁻. The positive ion CO₂ ice spectrum is characterized by R⁺ = C⁺, O⁺, CO⁺, O₂⁺ or CO₂⁺ and the negative one by R⁻ = CO₃⁻. The dominant series for ammonia ice correspond to R⁺ = NH₄⁺ and to R⁻ = NH₂⁻. The oxygen series are better described by (O₃)_nO_m⁺ secondary ions where m = 1, 2 or 3. Two positive ion series exist for N₂ ice: (N₂)_nN₂⁺ and (N₂)_nN⁺. For argon positive secondary ions, only the (Ar)_nAr⁺ series was observed. Most of the detected molecular ions were formed by one-step reactions. Ice temperature was varied from ∼20 K to complete sublimation.     

Coupling between the F-region and protonosphere: Numerical solution of the time-dependent equations

This paper describes a new method of solution of the time-dependent continuity and momentum equations for H⁺ and O⁺ in mid-latitude magnetic field tubes from the F-region to the equator. For each ion the equations are expressed as an integro-differential equation. This equation is treated as an ordinary differential equation and solved by a searching method. By means of this method, the distribution of H⁺ in the O⁺?H⁺ transition region and the protonosphere can be investigated and the influence of H⁺ fluxes on the F layer examined.As an example of application of the method a suggestion by Park (1971) about observed night-time enhancements of N_mF2 is examined. He suggested that lowering of the F layer some hours after a magnetic substorm may cause N_mF2 to increase because of increased ion influx from the protonosphere. In the present calculations the Flayer is maintained around a constant height for some time and then abruptly lowered. Under the conditions adopted the resulting increase in downward H⁺ flux is sufficient to maintain N_mF2 against the increased recombination but not to increase N_mF2 significantly. It is emphasised that these results are not conclusive.     

How much oxygen is too much? Constraining Saturn's ring atmosphere

The discovery of a molecular oxygen atmosphere around Saturn's rings has important implications for the electrodynamics of the ring system. Its existence was inferred from the Cassini in situ detection of molecular oxygen ions above the rings during Saturn Orbit Insertion in 2004. Molecular oxygen is difficult to observe remotely, and theoretical estimates have yielded only a lower limit (Nn?¹⁰¹³ cm⁻²) to the O₂ column density. Comparison with observations has previously concerned matching ion densities at spacecraft altitudes far larger than the scale height of the neutral atmosphere. This is further complicated by charged particle propagation effects in Saturn's offset magnetic field. In this study we adopt a complementary approach, by focusing on bulk atmospheric properties and using additional aspects of the Cassini observations to place an upper limit on the column density. We develop a simple analytic model of the molecular atmosphere and its photo-ionization and dissociation products, with Nn a free parameter. Heating of the neutrals by viscous stirring, cooling by collisions with the rings, and torquing by collisions with pickup ions are all included in the model. We limit the neutral scale height to h?3000 km using the INMS neutral density nondetection over the A ring. A first upper limit to the neutral column is derived by using our model to reassess O₂ production and loss rates. Two further limits are then obtained from Cassini observations: corotation of the observed ions with the planet implies that the height-integrated conductivity of the ring atmosphere is less than that of Saturn's ionosphere; and the nondetection of fluorescent atomic oxygen over the rings constrains the molecular column from which it is produced via photo-dissociation. These latter limits are independent of production and loss rates and are only weakly dependent on temperature. From the three independent methods described, we obtain similar limits: Nn?2×¹⁰¹⁵ cm⁻². The mean free path for collisions between neutrals thus cannot be very much smaller than the scale height.     

Computing molecular complexes in earth's and other atmospheres

There has been a considerable research interest in molecular aggregates, complexes or clusters, relevant to Earth's and other planetary atmospheres. Consequently, a considerable amount of data has been obtained in laboratory observations and also in computations. This report surveys our recent and ongoing computations of several such systems of atmospheric significancy, both systems with relatively weak and relatively strong bonding interactions. Among them, several types of homo- and hetero-dimers with importance to Earth's atmosphere: (H₂O)₂, (N₂)₂, N₂O₂, , (O₂)₂, or (O₃)₂. Dimer of carbon dioxide (CO₂)₂ is computed owing to its supposed significancy in the atmosphere of Venus. Systems with stronger bonding are represented by ClONO₂H⁺ and 2,3,7,8-tetrachlorodibenzo-p-dioxin. The report also discusses computational tools, combining advanced quantum-chemical methods with statistical-mechanical treatments. The structure, energetics, and vibrations of the complexes are evaluated at correlated ab initio levels. The computations typically show several minimum-energy structures and their relative populations are sensitive to temperature. The computed dimerization equilibrium constants are of a special interest as a critical stability measure and an input information for evaluations of the altitude population profiles in the atmosphere. A special attention is paid to the temperature enhancement of clustering degree in saturated vapors. This interesting paradox represents a product of atmospheric studies though it is actually a phenomenon of a more general physico-chemical validity.     

A model of the terrestrial ionosphere in the altitude interval 50–4000 km II. Molecular ions (N2 +, NO+, O2 +) and electron density

Empirical models of molecular ion densities (N₂ ⁺, NO⁺, O₂ ⁺) and the electron density (N _e ) are presented in the altitude interval 50–4000 km as functions of time (diurnal, annual), space (position, altitude) and solar flux (F _10.7). Using observations of 6 satellites (AE-C, AE-D, AE-E, ALOUETTE-2, ISIS-1, ISIS-2), 4 incoherent scatter stations (Arecibo, Jicamarca, Millstone Hill, St Santin) and more than 700 D-region profiles, this model describes the global gross features of the ionosphere for quiet geophysical conditions (K _p 3).The molecular ion densities and the electron density increase with increasing altitude up to a maximum (or several maxima) - and decrease from thereon with increasing height. Between ~80 and 200 km, the main ionic constituents are NO⁺ and O₂ ⁺; below ~80 km cluster ions are predominating. During local summer conditions the molecular ions and N _e increase around polar latitudes and decrease correspondingly during local winter. The diurnal variations are intrinsically coupled to the individual plasma layers; in general, the molecular ion and electron densities are enhanced during daytime and depleted during nighttime (for details and exceptions, see text).     

Ion chemistry in the cometary atmosphere

Dirty ice of a second kind (major components, H₂O, CO, and N₂; minor components less than several percents, NH₃, CH₄, and other organic substances such as HCN, CH₃CN etc.) is assumed for the composition of volatiles in the cometary nucleus. The consistency with the observations of molecular ions and daughter molecules in the cometary atmosphere is argued by taking into account various ion-molecular reactions and dissociative recombinations. There is a satisfactory agreement for the second kind of dirty-ice model, but the presence of large amounts of CH₄ and NH₃ is found to be rather in contradiction with observational evidence. A velocity of 8 km s^?1 for the hydrogen atoms, derived from analysis of the hydrogen Lyman-alpha corona around comets, is found from the dissociative recombination of H₃O⁺, the dominant constituent of cometary ionosphere, in accordance with H₃O⁺+e ^?→OH+H+H.     

Mid-latitude electron content modelling: The role of interhemispheric coupling

A modelling study of the electron content of the mid-latitude ionosphere and protonosphere has been carried out for solstice conditions using the mathematical model of Bailey (1983). In the model calculations coupled time-dependent O⁺, H⁺ continuity and momentum equations and O⁺, H⁺ and electron heat balance equations are solved for a magnetic shell extending over both hemispheres. The inclusion of interhemispheric flow of plasma and of heat balance has enabled us to investigate the role of interhemispheric coupling on the electron content and related shape parameters. The computed results are compared with results from slant path observations of the ATS-6 radio beacon made at Lancaster (U.K.) and Boulder, Colorado (U.S.A.).It has been found that the conjugate photoelectron heating has a major effect on the shape of the daily variation of slant slab thickness (τ) and also on the magnitude of the protonospheric content (N_p). Some of the main features of τ are closely related to the sunrise and sunset times in the conjugate ionosphere. Also it is found that night-time increases in total electron content (N_T) and F2 region peak electron density (N_max) in winter are natural consequences of ionization loss at low altitudes causing an enhanced downward flow of plasma from the protonosphere which is coupled to the summer hemisphere. One other important consequence of the coupled protonosphere is that the effects on N_T of the neutral air wind are not much different in winter from those in summer.     

On the dissociation of nitrogen by electron impact and by E.U.V. photo-absorption

The dissociation of N₂ by electron impact and by e.u.v. photo-absorption is studied, and it is shown that the forbidden predissociation of the numerous ¹Π_u and ¹Σ_u⁺ valence and Rydberg states of N₂ in the 11–24eV energy range is the dominant mechanism for N atom production. By measuring the absolute emission cross sections for the e.u.v. singlet bands of N₂ and by using the generalized oscillator strength data of Lassettre (1974), it has been possible to construct a detailed model of the total N₂ dissociation cross section which is in good agreement with the measurements of Winters (1966) and Niehaus (1967) and provides some insights into the maximum possible $\text{N(}{}^2\text{D)}$ yield from dissociative excitation. The total cross section for exciting N₂ e.u.v. radiation in the 800Å–1100Å wavelength range has been measured and found to have a value of 3.4 ×10^?17 cm² at 100 eV under optically thin conditions. Although this result implies that large fluxes of e.u.v. photons should be excited in auroral substorms and in the airglow, they are not observed, and we show that this development is a consequence of radiation entrapment and predissociation. The total cross section for dissociating N₂ by electron impact is given for optically thin and thick media. And some questions concerning the energy budget of a magnetospheric storm which are raised by these results, 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.     

Neutral temperatures and emission height changes in an E-region aurora

In this study a method is outlined which is capable of giving neutral temperatures and height changes in the aurora when the molecular emissions originate from the E-region.Absolute spectrometric measurements of N₂⁺ 1NG and O₂⁺ 1NG bands and the auroral green line are performed in a nightside aurora. Rotational temperatures and band intensities are deduced by a least-squares fit of synthetic spectra to observations. There is a close correlation between the variations in rotational temperatures and the relative intensity ratio of N₂⁺ 1NG(0,3) and O₂⁺ 1NG(1,0) bands. The change in the relative intensity ratio is similar to the intensity variation predicted by the changing N₂ and O₂ densities from 120 to 150 km, obtained from the MSIS 83 model atmosphere, and the derived neutral temperature variations are consistent with a similar change in emission height of the aurora. Therefore the changing temperature is most likely due to a changing emission height of the aurora, and no local heating can be inferred.     

Reaction paths leading from O+2 to water clusters under cold mesospheric conditions

Arnold and Krankowsky (Int. Symp. Solar-Terrestrial Physics, Sao Paulo, 1974) have reported D-region positive ion measurements in which a number of new cluster ions of minor abundance were apparent. These ions, which they attributed to clusters with N₂, O₂, and CO₂ ligands, were observable due to enhanced O⁺₂ production and to the low temperatures during the flight. Here we consider these in situ ion data in view of recent laboratory ion-molecule reaction experiments which cast light on the mechanism leading from O⁺₂ to water clusters in air mixtures. Possible intermediates are discussed in terms of ion stability and existence of effective reaction paths under the given atmospheric conditions. These proposed intermediates are then fitted into a coherent reaction mechanism resulting in significant new pathways for the formation of protonated water clusters. A semiquantitative measure of the importance of each of the pathways is then calculated by the use of signal flow graph theory.     

Geomagnetic storm effects on the thermosphere and the ionosphere revealed by in situ measurements from OGO 6

The temporal response of ion and neutral densities to a geomagnetic storm has been investigated on a global scale with data from consecutive orbits of OGO-6 (>400km) for 4 days covering both magnetically quiet and disturbed conditions. The first response of the neutral atmosphere to the storm takes place in the H and He densities which start to decrease near the time of the storm sudden commencement. The maximum decreases in H and He were more than 40% of the normal density at high latitudes. A subsequent increase in O and N₂ densities occurs about 8 hours later than the change in H and He densities, while the relative O and N₂ density changes indicate a depletion of atomic oxygen in the lower thermosphere by more than a factor of two. The overall features of the change in the neutral atmosphere, especially the patterns of change for individual species, strongly support the physical picture that energy is deposited primarily at high latitudes during the storm, and the thermosphere structure changes through (1) heating of the lower thermosphere and (2) generation of large scale circulation in the atmosphere with upwelling at high latitudes and subsidence at the equator. The storm-time response of H⁺ occurs in two distinct regions separated by the low latitude boundary of the light ion trough. While on the poleward side of the boundary the H⁺ density decreases in a similar manner to the decrease in H density, on the equatorward side of the boundary the H⁺ decrease occurs about half a day later. It is shown that the decrease of H⁺ density is principally caused by the decrease in H density for both regions. The difference in H⁺ response between the two regions is interpreted as the difference in H⁺ dynamics outside and inside the plasmasphere. The O⁺ density shows an increase, the pattern of which is rather similar to that for O. Two possibilities for explaining the observed change in O⁺ density are suggested. One attributes the observed increase in O⁺ density to an increase in the plasma temperature during the storm. The other possibility is that the increase in the production rate of O⁺ due to an increase in O density exceeds the increase in the loss rate of O⁺ due to an increase in N₂ density, especially around the time of sunrise. Hence the change in O⁺ density in the F-region may actually be controlled by the change in O density.     

Formation of Dust Grains in Circumstellar Envelopes of Oxygen-Rich AGB Stars

We discuss dust formation in steady state dust driven winds around oxygen-rich AGB stars, including not only homogeneous Al₂O₃ and silicate grains but also heterogeneous grains consisting of an Al₂O₃ core and a silicate mantle. In the inner subsonic region, Al₂O₃ grains with radii of ∼ 0.15 μm condense first, then condensation of silicate on Al₂O₃ starts slightly inside the sonic point, which accelerates the gas flow into the supersonic region. Also small silicate grains, whose radii are a few tens of ?ngstroms form beyond the sonic point. The carrier of 13 μm feature observed towards oxygen-rich AGB stars is considered to be the core-mantle grains consisting of an α-Al₂O₃ core and a silicate mantle from the radiation transfer calculations based on the results of dust formation calculations. This revised version was published online in September 2006 with corrections to the Cover Date.