Fluorescence efficiencies of electrons in second positive bands of N2 and first negative bands of N2+

Fluorescence efficiencies of electrons in a large number of bands of N₂ second positive and N_2⁺ first negative groups lying in the 3000–5200 Å region are calculated. At very low pressure where quenching is negligible the present values are within 15 per cent of the experimental data of Hartmann (1968). The efficiencies are found to be independent of the impact energies greater than 200 eV which is in accordance with other theoretical and experimental results. The ratio of the total efficiencies in N₂ second positive and N_2⁺ first negative groups is 1·31 and is about 20 per cent lower than the experimental values. The efficiencies at a higher pressure equal to 600 torr are compared with the experimental data of Davidson and O'Neil (1964a).     

The height,spectrum and mechanism of type-B red aurora and its bearing on the excitation of O(1S) in aurora

The height of the lower red border of type-B aurora has been determined by triangulation using TV cameras at two ground stations. A mean height of 91.4 ± 1.1 km was determined from a set of 12 measurements made under ideal conditions. A TV spectrograph was used simultaneously to seek possible spectral changes between 6400 and 6900 Å which would be indicative of changes in the vibrational distribution in the N₂ First Positive bands. No significant difference was found in this distribution between the spectra from 93 and 122 km. The height distribution of contributions to the OI 5577 Å emission relative to the N⁺₂ First Negative emission was modelled from 80 to 160 km. Contributions from electron impact on atomic O, O⁺₂ dissociative recombination and N₂(A)O energy transfer were included. Account was taken of recent laboratory data on O(¹S) quenching. It was concluded that these processes could explain the excitation of O(¹S) in normal aurora and the height distribution of OI 5577 Å in type-B red aurora. It was confirmed that the lifetime ofO(¹S) in type-B red auroral rapid time variations is about 0.5 s and it was found from the model that the observed time variation can be reproduced by the mechanisms considered, provided the concentration of NO in the auroral atmosphere is about 1 × 10⁹ at 95 km. Before reasonable certainty can be attained in the correctness of the interpretation it will however be necessary to have reliable simultaneous observations of neutral atmospheric composition particularly for O and NO as well as unchallengeable measurements of the yields of O(¹S) for the processes considered and for several other processes which have been suggested recently.     

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.     

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.     

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.     

Modeling of the N2+ First negative bands in the sunlit aurora

The N_2⁺ First Negative band profiles in the high-altitude sunlit aurora are modeled by solving a set of simultaneous coupled equations for the population and depopulation of the N_2⁺ vibrational and rotational energy levels. Approximations due to computer processing time and the use of1-→A averaged solar flux resulted in the loss of the Swings effect, but otherwise the modeled spectra simulate the observations and the characteristic high rotational development quite closely. Comparisons with the well-known spectrum of the 3914 Å band in the sunlit auroral ray published by Hunten et al. (1959, Nature 183, 453) give the N_2⁺ ion lifetime of ∼10³ s and N₂X rotational temperature of ∼600 K, and are consistent with the fluorescent excitation mechanism; this contradicts conclusions made some two decades ago. A sample auroral cusp spectrum is included to illustrate the effects of Rayleigh scattering of solar flux.     

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.     

Mass composition of the escaping plasma at Mars

Data from the Ion Mass Analyzer (IMA) sensor of the ASPERA-3 instrument suite on Mars Express have been analyzed to determine the mass composition of the escaping ion species at Mars. We have examined 77 different ion-beam events and we present the results in terms of flux ratios between the following ion species: CO⁺₂/O⁺ and O⁺₂/O⁺. The following ratios averaged over all events and energies were identified: CO⁺₂/O⁺ = 0.2 and O⁺₂/O⁺ = 0.9. The values measured are significantly higher, by a factor of 10 for O⁺₂/O⁺, than a contemporary modeled ratio for the maximum fluxes which the martian ionosphere can supply. The most abundant ion species was found to be O⁺, followed by O⁺₂ and CO⁺₂. We estimate the loss of CO⁺₂ to be by using the previous measurements of Phobos-2 in our calculations. The dependence of the ion ratios in relation to their energy ranges we studied, 0.3-3.0 keV, indicated that no clear correlation was found.     

Intensity ratio I(5577)/I(3914) in morning and evening pulsating aurora

The ratio of the intensity of the oxygen green line at 5577 A to that of the N₂⁺ First Negative band (0, 0) at 3914 A in morning and evening pulsating aurora has been observed using a ground-based scanning photometer which scans the entire sky in 2.6 sec with 2° resolution.The ratio I(5577)/I(3914), after corrections for scattering and extinction made on the basis of hemispheric averages of the intensities at each wavelength, is up to 50% lower in the pulsations than in the surrounding diffuse aurora and in pre-breakup discrete auroras. In morning pulsations this ratio showed systematic decreases with time and with increasing intensity.We report here what we believe to be the first quantitative intensity measurements made of the rare phenomenon evening pulsations. These also show a reduced ratio and a tendency for the ratio to decrease with time.The range of previously published values of the 5577 A time constant in pulsating auroras would lead to ratio variations of the same magnitude as those reported here, suggesting that quenching effects may be more important than atmospheric composition changes in determining intensity ratios within the altitude range of pulsating auroras.     

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.     

The dayside Venus ionosphere: I. Pioneer-Venus retarding potential analyzer experimental observations

The median values of the principal ionospheric quantities of the Venus dayside ionosphere are presented. The values are derived from the quantities measured by the Pioneer-Venus orbiter retarding potential analyzer over a period of two Earth yaers at solar cycle maximum. Quantities reported are total ion density, O⁺ density, O₂⁺ density, sum density (NO⁺ + N₂⁺ + CO⁺), CO₂⁺ density, ion temperature, electron temperature, and plasma particle pressure. The data are organized to reveal altitude, solar zenith angle, solar longitude, and latitude dependences. The O⁺ density exhibits both a solar longitude and a latitude dependence which we suggest is caused by superrotation of the thermosphere and/or ionosphere. Asymmetry between the dawn and dusk terminator regions in the behavior of other quantities is also descibed.     

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.     

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.     

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.     

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.     

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.     

Ion composition and chemistry in the coma of Comet 1P/Halley—A comparison between Giotto's Ion Mass Spectrometer and our ion-chemical network

In order to understand the cometary plasma environment it is important to track the closely linked chemical reactions that dominate ion evolution. We used a coupled MHD ion-chemistry model to analyze previously unpublished Giotto High Intensity Ion Mass Spectrometer (HIS-IMS) data. In this way we study the major species, but we also try to match some minor species like the CH_x and the NH_x groups. Crucial for this match is the model used for the electrons since they are important for ion-electron recombination. To further improve our results we included an enhanced density of supersonic electrons in the ion pile-up region which increases the local electron impact ionization. In this paper we discuss the results for the following important ions: C⁺, CH⁺, CH⁺₂, CH⁺₃, N⁺, NH⁺, NH⁺₂, NH⁺₃, NH⁺₄, O⁺, OH⁺, H₂O⁺, H₃O⁺, CO⁺, HCO⁺, H₃CO⁺, and CH₃OH⁺₂. We also address the inner shock which is very distinctive in our MHD model as well as in the IMS data. It is located just inside the contact surface at approximately 4550 km. Comparisons of the ion bulk flow directions and velocities from our MHD model with the data measured by the HIS-IMS give indication for a solar wind magnetic field direction different from the standard Parker angle at Halley's position. Our ion-chemical network model results are in a good agreement with the experimental data. In order to achieve the presented results we included an additional short lived inner source for the C⁺, CH⁺, and CH⁺₂ ions. Furthermore we performed our simulations with two different production rates to better match the measurements which is an indication for a change and/or an asymmetric pattern (e.g. jets) in the production rate during Giotto's fly-by at Halley's comet.     

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.     

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.     

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.