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

Martin Rubin  Kenneth C. Hansen  Michael R. Combi  Hans Balsiger 《Icarus》2009,199(2):505-519

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 We used a coupled MHD ion-chemistry model to analyze previously unpublished Giotto High Intensity Ion Mass Spectrometer (HIS-IMS) data.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.  相似文献   

Radial distribution of production rates, loss rates and densities corresponding to ion masses ?40 amu in the inner coma of Comet Halley: Composition and chemistry     

S.A. Haider 《Icarus》2005,177(1):196-216

In this paper we have studied the chemistry of C, H, N, O, and S compounds corresponding to ions of masses ?40 amu in the inner coma of the Comet 1P/Halley. The production rates, loss rates, and ion mass densities are calculated using the Analytical Yield Spectrum approach and solving coupled continuity equation controlled by the steady state photochemical equilibrium condition. The primary ionization sources in the model are solar EUV photons, photoelectrons, and auroral electrons of the solar wind origin. The chemical model couples ion-neutral, electron-neutral, photon-neutral and electron-ion reactions among ions, neutrals, electrons, and photons through over 600 chemical reactions. Of the 46 ions considered in the model the chemistry of 24 important ions (viz., CH₃OH⁺₂, H₃CO⁺, NH⁺₄, H₃S⁺, H₂CN⁺, H₂O⁺, NH⁺₃, CO⁺, C₃H⁺₃, OH⁺, H₃O⁺, CH₃OH⁺, C₃H⁺₄, C₂H⁺₂, C₂H⁺, HCO⁺, S⁺, CH⁺₃, H₂S⁺, O⁺, C⁺, CH⁺₄, C⁺₂, and O⁺₂) are discussed in this paper. At radial distances <1000 km, the electron density is mainly controlled by 6 ions, viz., NH⁺₄, H₃O⁺, CH₃OH⁺₂, H₃S⁺, H₂CN⁺, and H₂O⁺, in the decreasing order of their relative contribution. However, at distances >1000 km, the 6 major ions are H₃O⁺, CH₃OH⁺₂, H₂O⁺, H₃CO⁺, C₂H⁺₂, and NH⁺₄; along with ions CO⁺, OH⁺, and HCO⁺, whose importance increases with further increase in the radial distance. It is found that at radial distances greater than ∼1000 km (±500 km) the major chemical processes that govern the production and loss of several of the important ions in the inner coma are different from those that dominate at distances below this value. The importance of photoelectron impact ionization, and the relative contributions of solar EUV, and auroral and photoelectron ionization sources in the inner coma are clearly revealed by the present study. The calculated ion mass densities are compared with the Giotto Ion Mass Spectrometer (IMS) and Neutral Mass Spectrometer (NMS) data at radial distances 1500, 3500, and 6000 km. There is a reasonable agreement between the model calculation and the Giotto measurements. The nine major peaks in the IMS spectra between masses 10 and 40 amu are reproduced fairly well by the model within a factor of two inside the ionopause. We have presented simple formulae for calculating densities of the nine major ions, which contribute to the nine major peaks in the IMS spectra, throughout the inner coma that will be useful in estimating their densities without running the complex chemical models.  相似文献   

Magnesium ion chemistry in the stratosphere     

E.E. Ferguson  B.R. Rowe  D.W. Fahey  F.C. Fehsenfeld 《Planetary and Space Science》1981,29(4):479-481

Laboratory measurements of reaction rate constants of magnesium ions and magnesium containing ions with O₃, NO, HNO₃, and H₂O₂ have been carried out in a flowing afterglow experiment. Mg⁺ ions react with O₃ to produce MgO⁺ ions, which in turn react with O₃ to produce Mg⁺ ions. Mg⁺ ions react with HNO₃ and H₂O₂ to produce MgOH⁺ ions. MgOH⁺ ions react rapidly with HNO₃ to produce NO⁺₂ ions and Mg(HO)₂. One can therefore conclude that Mg⁺, MgO⁺, or MgOH⁺ ions could not have significant concentrations in the stratosphere if gas phase magnesium compounds were present. The failure to observe these ions therefore cannot be used as evidence that the stratospheric magnesium, resulting from meteor ablation at higher altitudes, is in condensed phases. This is in contrast to the case for sodium where the ion chemistry is such that the failure to observe hydrated Na⁺ ions proves that gas phase sodium compounds are not present in the stratosphere.  相似文献   

The role of hydrocarbons in the lonospheres of the outer planets     

S.K. Atreya  T.M. Donahue 《Icarus》1975,25(2):335-338

The role of hydrocarbons as a possible sink for H⁺ and H₃⁺ ions in the lower ionosphere of the outer planets is examined. Calculations indicate that H⁺ and H₃⁺ are efficiently converted to hydrocarbon ions on reaction with methane. The terminal ions, CH₅⁺ and C₂H₅⁺ are rapidly neutralized in dissociative recombination with electrons. Extreme ultraviolet photolysis of hydrocarbons as a potential additional source of lower elevation ions in investigated.  相似文献   

Measurements of positive ion conversion and removal reactions relating to the Jovian ionosphere     

Rainer Johnsen  Manfred A. Biondi 《Icarus》1974,23(2):139-143

Measured rates are presented for the reaction of He⁺ ions with H₂ (and D₂) molecules to form H⁺, H₂⁺, and HeH⁺ ions, as well as for the subsequent reactions of H⁺ and HeH⁺ ions with H₂ to form H₃⁺. The neutralization of H₃⁺ (and H₅⁺) ions by dissociative recombination with electrons is shown to be fast. The reaction He⁺ + H₂ is slow (k = 1.1 × 10^?13 cm³/sec at300°K) and produces principally H⁺ by the dissociative charge transfer branch. It is concluded that there may be a serious bottleneck in the conversion of two of the primary ions of the upper Jovian ionosphere, H⁺ and He⁺ (which recombine slowly), to the rapidly recombining H₃⁺ ion (α[H₃⁺]?3.4 × 10^?7 cm³/sec at 150°K).  相似文献   

Mass composition of the escaping plasma at Mars     

E. Carlsson  A. Fedorov  E. Budnik  H. Gunell  J.-A. Sauvaud  Y. Futaana  H. Andersson  J.D. Winningham  J.R. Sharber  A.J. Coates  D.O. Kataria  H. Koskinen  P. Riihelä  J. Kozyra  E. Roelof  S. Livi  K.C. Hsieh  M. Grande  J.-J. Thocaven  S. Orsini  M. Maggi  P. Bochsler  J. Woch  K. Asamura 《Icarus》2006,182(2):320-328

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.  相似文献   

Mass spectrometer measurements of the positive ion composition in the D- and E-regions of the ionosphere     

P. A. Zbinden  M. A. Hidalgo  P. Eberhahdt  J. Geiss 《Planetary and Space Science》1975,23(12):1621-1642

On 14 December 1971, during the maximum of the Geminid Meteor Shower, the positive ion composition was measured in the D- and E-regions above Sardinia. The payload was launched at 12:11 UT, and measurements were made between 68.5 and 152 km altitude. A magnetic sector type mass spectrometer with dual collector and a liquid helium cryopump was used. The instrument covered the mass range from 11 to 73 AMU and had a resolution at the 1 % level of M/ΔM = 60.In the E-region two distinct metal ion layers were observed, centred at 95 and 119 km, respectively. In the lower layer Fe⁺ and Mg⁺ were the most abundant metal ions, and in the upper layer Si⁺ was dominant. Si⁺ ions were conspicuously absent in the lower layer (Si⁺/Mg⁺ < 2 × 10⁻³). This particular behaviour of Si could be due to the inability of atomic oxygen to reduce SiO, whereas in the upper layer Si⁺ions might be formed directly by the charge rearrangement reaction SiO + O⁺ → Si⁺+ O₂. In addition, Na⁺, Al⁺, K⁺, Ca⁺, Ti⁺, Cr⁺, Ni⁺ and Co⁺ were also identified. The metal oxide ions AlO⁺ and SiO⁺ were detected, and probably also MgO⁺ and SiOH⁺. The concentrations of NO⁺ and O₂⁺ show a deep minimum at the maximum of the lower metal ion layer. A very high neutral metal density of 6 × 10⁷ cm⁻³ would be required to explain this feature as resulting from charge transfer reactions between the molecular and metal ions Such a high metal density is in contradiction to direct measurements and to cosmic dust influx rates. The isotopic ratios of Mg⁺, Si⁺, and of the major isotopes of Fe⁺ and Ni⁺ were measured, some of them with an accuracy of a few per cent (²⁵Mg⁺/²⁴Mg⁺ = 0.124 ± 0.006; ²⁶Mg⁺/²⁴Mg⁺ = 0.139 ± 0.008; ²⁹Si⁺/²⁸Si⁺ = 0.050 ± 0.004; ⁵⁴Fe⁺/⁵⁶Fe⁺ = 0.069 ± 0.005; ⁵⁷Fe⁺/⁵⁶Fe⁺ = 0.029 ± 0.004; ⁶⁰Ni⁺/⁵⁸Ni⁺ = 0.31 ± 0.12). The isotopic ratios agree within the experimental errors with the corresponding terrestrial ratios, thus giving evidence that these elements have the same isotopic composition in the Geminid meteors as in the Earth's crust, in chrondrites, and in lunar material.In the D-region the ions Na⁺H₂O, Na⁺(H₂O)₂, NaO⁺ and NaOH⁺ were tentatively identified. Below 95 km altitude the relative abundances of the ions 32⁺, 33⁺ and 34⁺ deviate from the values expected for molecular oxygen isotopes. Their abundances can not be explained by the presence of S-ions only, and we conclude that HO₂⁺ and H₂O₂⁺ are present.The ion density profiles of the major D-region constituents show some remarkable deviations from typical D-region conditions. These deviations are related to the winter anomaly in ionospheric absorption observed over Spain during the launch day, and our data represent the first ion composition measurements during such conditions. In particular, H⁺(H₂O)₂ is the major ion only up to 77 km, and at 80 km altitude the NO⁺ concentration exceeds the total water cluster ion density by almost two orders of magnitude. An increase of the mesospheric NO, O₃ and O concentrations as well as of the O/H₂O ratio could explain the observed ion profiles. The low NO⁺/O₂⁺ ratios of approximately unity measured in the E-region are in agreement with a strong downward transport of NO and/or O into the mesosphere during the launch day. A simple four-ion model was used to interpret our D-region data. The calculated neutral NO concentration increases from about 2 × 10⁷ cm⁻³ at 85 km to 5 × 10⁷ cm⁻³ at 80 km. In addition, evidence for an increased O₂⁺ production rate above 83 km was found, probably due to an enhanced O₃ concentration. We conclude that our data strongly support vertical transport of minor neutral consituents as cause of the winter anomaly.  相似文献   

Structure and time variations of the Jovian ionosphere     

T. Tanaka  K. Hirao 《Planetary and Space Science》1973,21(5):751-762

The problem of the ionospheric formation in the Jovian upper atmosphere is examined. By adopting two plausible atmospheric models, we solve coupled time-dependent continuity equations for ions H₂⁺, H₅⁺, H⁺, H₃⁺ and H_eH⁺ simultaneously. It is shown that both radiative and three body association of H⁺ to H₂ are important for the determination of the structure of the Jovian ionosphere. The maximum electron density in the daytime is found to be about 10⁵ cm^?3. It is also shown that diurnal variation with large-amplitude can exist in the Jovian ionosphere.  相似文献   

Electronic Sputtering Analysis of Astrophysical Ices     

L. S. Farenzena  P. Iza  R. Martinez  F. A. Fernandez-Lima  E. Seperuelo Duarte  G. S. Faraudo  C. R. Ponciano  M. G. P. Homem  A. Naves de Brito  K. Wien  E. F. da Silveira 《Earth, Moon, and Planets》2005,97(3-4):311-329

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.  相似文献   

The upper ionosphere of Titan     

R.C. Whitten  L.A. Capone  L. McCulley  P.F. Michelson 《Icarus》1977,31(1):89-96

Photoionization of the upper atmosphere of Titan by sunlight is expected to produce a substantial ionospheric layer. We have solved one-dimensional forms of the mass, momentum, and energy conservation equations for ions and electrons and have obtained electron number densities of about 10³ cm^?3, using various model atmospheres. The significant ions in a CH₄H₂ atmosphere are H⁺, H₃⁺, CH₅⁺, CH₅⁺, CH₃⁺, and C₂H₅⁺. Electron temperatures may be as high as 1000°K, depending on the abundance of hydrogen in the high atmosphere. Interaction of the solar wind with the ionosphere is also discussed.  相似文献   

A fast computation of the diurnal secondary ion production in the ionosphere of Titan     

Jean Lilensten  Cyril Simon  Odile Dutuit  Christian Alcaraz 《Icarus》2005,174(1):285-288

We propose an analytic model that allows rapid computation of the secondary ion production due to electron impact from the primary photo-production in the ionosphere of Titan. The model parameters are given for each of the 5 major ion productions (N⁺₂, CH⁺₄, N⁺, CH⁺₃, N⁺⁺₂) as well as for the electron production.  相似文献   

Models of the cometary coma in which abundances are calculated for various heliocentric distances     

Michael B. Swift  George F. Mitchell 《Icarus》1981,47(3):412-430

One-dimensional radial models of the chemistry in cometary comae have been constructed for heliocentric distances ranging from 2 to 0.125 AU. The coma's opacity to solar radiation is included and photolytic reaction rates are calculated. A parent volatile mixture similar to that found in interstellar molecular clouds is assumed. Profiles through the coma of number density and column density are presented for H₂O, OH, O, CN, C₂, C₃, CH, and NH₂. Whole-coma abundances are presented for NH₂, CH, C₂, C₃, CN, OH, CO⁺, H₂O⁺, CH⁺, N₂⁺, and CO₂⁺.  相似文献   

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

H. Böhringer  M. Durup-Ferguson  E.E. Ferguson  D.W. Fahey 《Planetary and Space Science》1983,31(4):483-487

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.  相似文献   

Representative abundances of a few positive ions in the innermost coma of comet Halley     

P. P. Saxena  Alka Misra 《Earth, Moon, and Planets》1993,60(1):59-68

The production rate of H₂O molecules at a heliocentric distance of 1 AU for comet Halley and the abundance ratio with respect to water (H₂O) of parent molecules at the cometary nucleus from the paper of Yamamoto (1987) have been used to compute the number densities of positive ions viz. H₃O⁺, H₃S⁺, H₂CN⁺, H₃CO⁺, CH₃OH ₂ ⁺ and NH ₄ ⁺ at various cometocentric distances within 600 kms from the nucleus.The role of proton transfer reactions in producing major ionic species is discussed. A major finding of the present investigation is that NH ₄ ⁺ ion which may be produced through proton transfer reactions is the most abundant ion near the nucleus of a comet unless the abundance of NH₃ as a parent is abnormally low. Using the quoted value of Q(NH₃)/Q(H₂O) for comet Halley and the life times of NH₃ and H₂O molecules, the abundance ratio N(NH₃)/N(H₂O) is found to be one-third of that used in the present paper. The consequent proportionate decrease in the NH ₄ ⁺ ions does not, however, affect its superiority in number density over other ions near the nucleus.The number density of the next most abundant ion viz. H₃O⁺ is found to be 4 × 10⁴ cm^-3 at the nucleus of comet Halley and decreases by a factor of two only upto a distance of 600 K ms from the nucleus. The ionic mass peak recorded by VEGA and GIOTTO spacecrafts atm/q = 18 is most probably composite of the minor ionic species H₂O⁺, as its number density = 10² cm^-3 remains virtually constant in the inner coma and of NH ₄ ⁺ , the number density of which at large cometocentric distances may add to the recorded peak atmlq = 18. The number densities of other major ions produced through proton transfer from H₃O⁺ are also discussed in the region within 600 K ms from the nucleus of comet Halley.  相似文献   

Measured ion-molecule reaction rates for modelling Titan's atmosphere     

Seksan Dheandhanoo  Rainer Johnsen  Manfred A. Biondi 《Planetary and Space Science》1984,32(10):1301-1305

Rate coefficients for several two- and three-body ion-molecule reactions involving hydrocarbons have been determined at thermal energies and above using drift tube-mass spectrometer techniques. The measured rates for clustering and breakup reactions involving CH₅⁺ and C₂H₅⁺ ions in methane are found to be strongly temperature dependent in the range from 80 to 240 K. The equilibrium constants determined for these reactions differ somewhat from those of Hiraoka and Kebarle. Rate coefficients for two-body reactions of CH₅⁺, C₂H₅⁺, N⁺, H⁺ and D⁺ ions with methane and/or ethane have been measured. The results indicate that the product yields of several of the fast ion-molecule reactions depend strongly on ion energy (temperature), and therefore previous room-temperature results may be of limited value for model calculations of Titan's atmosphere.  相似文献   

Effects of low concentrations of O2 and CO on the ion-clustering reactions in the lower ionosphere of Mars     

L.W. Sieck  R. Gorden  P. Ausloos 《Planetary and Space Science》1973,21(11):2039-2041

It is demonstrated that under conditions which approximate those of the Martian ionosphere traces of CO and O₂ can be effectively incorporated in ion clusters via ion-molecule reaction schemes initiated by the CO₂⁺ ion. For example, when 0.3 % CO is added to CO₂, (CO)₂⁺ and [(CO)₂CO₂]⁺ appear as the major cations (584 Å radiation, 300°K). In mixtures containing O₂ in addition to CO₂ (CO₂. O₂)⁺ and [(CO₂)₂O₂]⁺ are important species. A recently proposed mechanism to account for the low abundance of CO and O₂ in the Martian atmosphere is discussed in the light of these observations.  相似文献   

Ionospheric composition in SAR-arcs     

W.J. Raitt  R.W. Schunk  P.M. Banks 《Planetary and Space Science》1976,24(2):105-114

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.  相似文献   

Silicon ion chemistry in the ionosphere     

E.E. Ferguson  D.W. Fahey  F.C. Fehsenfeld  D.L. Albritton 《Planetary and Space Science》1981,29(3):307-312

Loss processes which remove Si⁺ ions selectively relative to other meteor-derived atomic ions in the E- and D-regions of the ionosphere have been identified and measured in the laboratory. The major Si⁺ loss in the E-region is the reaction Si⁺ + H₂O → HSiO⁺ + H (1) with a rate constant 2.3 ± 0.9 × 10^?10 cm³s^?1 at 300 K. The corresponding reactions with Fe⁺, Mg⁺ and other metallic meteor ions are endothermic. Presumably (1) is followed by a fast dissociative-recombination with electrons to produce neutral SiO or Si. At lower altitudes Si⁺ ions associate in a three-body reaction with O₂ with a much larger rate constant than the corresponding associations of Fe⁺ and Mg⁺ with O₂.  相似文献   

Calculations of the thermochemistry of six reactions leading to ammonia formation in Titan's atmosphere     

Su-hong Ge  Xin-lu Cheng  Xiang-dong Yang  Wei Wang 《Icarus》2006,183(1):153-158

The thermochemical properties of the six reactions: (1) N₂+hν (solar EUV) → N⁺ + N(⁴S) + e⁻, (2) N⁺ + H₂ → NH⁺ + H, (3) NH⁺ + H₂ → NH⁺₂ + H, (4) NH⁺₂ + H₂ → NH⁺₃ + H, (5) NH⁺₃ + H₂ → NH⁺₄ + H, and (6) NH⁺₄ + e⁻ → NH₃ + H, were theoretically proposed by Atreya in 1986 and were cited in 2003 by Bernard who assumed that this chain reaction would lead to ammonia formation in Titan's atmosphere. The thermochemical properties of these six reactions have been calculated by means of the coupled cluster singles and doubles (CCSD) at the CCSD/cc-pvdz level, and the CCSD/6-311++g(3df,3pd) level, and G2 method. The geometries of the reactants and products of reactions have been optimized, the energies of reactions have been computed. The analysis of the results shows that: (I) The free energies of four reactions among these six reactions are negative. It means that these reactions, namely reactions (1)-(6) except reaction (2), can react spontaneously in Titan's low temperature environment. The converted temperatures of reactions (3) and (5) are 11881.7 and 4596.9 K, respectively. (II) Reaction (2) is an endothermic reaction, its converted temperature is 1797.6 K. When T<1797.6 K, reaction (2) cannot react forward spontaneously. The barrier of reaction (2) is 26.154 kcal mol⁻¹, which is probably too high to allow it to occur in the atmosphere of Titan. The rate for this reaction at 300 K has been calculated, and the value is k=4.16×¹⁰⁻⁷ s⁻¹. (III) The results of the three methods are more or less the same. So it is concluded that this chain reaction cannot be a pathway to lead to ammonia (gas phase) formation in Titan's atmosphere.  相似文献   

Effects of ion excitation on charge transfer reactions of the Mars, Venus, and Earth ionospheres   总被引：1，自引：0，他引：1  

C. Nicolas  C. Alcaraz  R. ThissenJ. Zabka  O. Dutuit 《Planetary and Space Science》2002,50(9):877-887

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.  相似文献