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1.
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   

2.
Laboratory measurements of the reaction of O2+ with NO from thermal energy to 0.6 eV in an Ar buffered flow drift tube agree with similar measurements made earlier in the same drift tube with He buffer. Since the O2+ ions are substantially vibrationally excited in Ar and not in He it follows that the reaction is not enhanced by vibrational excitation of the O2+.  相似文献   

3.
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.  相似文献   

4.
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 XnR±, 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)nOm+ 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   

5.
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   

6.
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   

7.
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   

8.
We have performed a numerical simulation to analyze the energy spectra of escaping planetary O+ and O2+ ions at Mars. The simulated time-energy spectrograms were generated along orbit no. 555 (June 27, 2004) of Mars Express when its Ion Mass Analyzer (IMA)/ASPERA-3 ion instrument detected escaping planetary ions. The simulated time-energy spectrograms are in general agreement with the hypothesis that planetary O+ and O2+ ions far from Mars are accelerated by the convective electric field. The HYB-Mars hybrid model simulation also shows that O+ ions originating from the ionized hot oxygen corona result in a high-energy (E>1 keV) O+ ion population that exists very close to Mars. In addition, the simulation also results in a low-energy (E<0.1 keV) planetary ion population near the pericenter. In the analyzed orbit, IMA did not observe a clear high-energy planetary ion or a clear low-energy planetary ion population near Mars. One possible source for this discrepancy may be the Martian magnetic crustal anomalies because MEX passed over a strong crustal field region near the pericenter, but the hybrid model does not include the magnetic crustal anomalies.  相似文献   

9.
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.  相似文献   

10.
The sunlit portion of planetary ionospheres is sustained by photoionization. This was first confirmed using measurements and modelling at Earth, but recently the Mars Express, Venus Express and Cassini-Huygens missions have revealed the importance of this process at Mars, Venus and Titan, respectively. The primary neutral atmospheric constituents involved (O and CO2 in the case of Venus and Mars, O and N2 in the case of Earth and N2 in the case of Titan) are ionized at each object by EUV solar photons. This process produces photoelectrons with particular spectral characteristics. The electron spectrometers on Venus Express and Mars Express (part of ASPERA-3 and 4, respectively) were designed with excellent energy resolution (ΔE/E=8%) specifically in order to examine the photoelectron spectrum. In addition, the Cassini CAPS electron spectrometer at Saturn also has adequate resolution (ΔE/E=16.7%) to study this population at Titan. At Earth, photoelectrons are well established by in situ measurements, and are even seen in the magnetosphere at up to 7RE. At Mars, photoelectrons are seen in situ in the ionosphere, but also in the tail at distances out to the Mars Express apoapsis (∼3RM). At both Venus and Titan, photoelectrons are seen in situ in the ionosphere and in the tail (at up to 1.45RV and 6.8RT, respectively). Here, we compare photoelectron measurements at Earth, Venus, Mars and Titan, and in particular show examples of their observation at remote locations from their production point in the dayside ionosphere. This process is found to be common between magnetized and unmagnetized objects. We discuss the role of photoelectrons as tracers of the magnetic connection to the dayside ionosphere, and their possible role in enhancing ion escape.  相似文献   

11.
A spectrum of Mars of unprecedented quality was obtained in the range of 904-1183 Å with a spectral resolution of 0.2 Å using the Far Ultraviolet Spectroscopic Explorer. Besides marking the first detection of molecular hydrogen on Mars (Krasnopolsky and Feldman, Science 2001 294, 1914-1917), the spectrum also revealed many emission lines of H, O, N, C, Ar, He, N+, C+, and Ar+ and the bands of N2 and CO. The spectrum makes it possible to study the emission multiplet structures and the component ratios and to separate many of the blended lines. From the argon lines, we retrieved Ar mixing ratios of 1.5 and 1.3% at 150 and 130 km, respectively, in excellent agreement with the Viking mass spectrometric measurements of 1.6% in the lower atmosphere. The He 584-Å emission observed in second order also agrees with the Extreme Ultraviolet Explorer detection of He on Mars. The observed spectrum may be used as a database to study specific problems such as the dayglow excitation, radiative transfer, and composition in Mars' upper atmosphere.  相似文献   

12.
Hydrogen is the most abundant element in the universe. Molecular hydrogen is the dominant chemical species in the atmospheres of the giant planets. Because of their low masses, neutral and ionized hydrogen atoms are the dominant species in the high atmospheres of many planets. Finally, protons are the principal heavy component of the solar wind.Here we present a critical evaluation of the current state of understanding of the chemical reaction rates and collision cross sections for several important hydrogen collision processes in planetary atmospheres, ionospheres, and magnetospheres. Accurate ab initio quantum theory will play an important role. The collision processes are grouped as follows:
(a)
H++H charge transfer,
(b)
H++H2(v) charge transfer and vibrational relaxation, and
(c)
H2(v,J)+H2 vibrational, rotational, and ortho-para relaxation.
In each case we provide explicit representations as tabulations or compact formulas. Particularly important conclusions are that H++H2(v) collisions are more likely to result in vibrational relaxation than charge transfer and H2 ortho-para conversion is at least an order-of-magnitude faster than previously assumed.  相似文献   

13.
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.  相似文献   

14.
A scheme of excitation, quenching, and energy transfer processes in the oxygen nightglow on the Earth, Venus, and Mars has been developed based on the observed nightglow intensities and vertical profiles, measured reaction rate coefficients, and photochemical models of the nighttime atmospheres of the Venus and Mars. The scheme involves improved radiative lifetimes of some band systems, calculated yields of the seven electronic states of O2 in termolecular association, and rate coefficients of seven processes of electronic quenching of the Herzberg states of O2, which are evaluated by fitting to the nightglow observations. Electronic quenching of the vibrationally excited Herzberg states by O2 and N2 in the Earth's nightglow is a quarter of total collisional removal of the O2(A, A′) states and a dominant branch for the O2(c) state. The scheme supports the conclusion by Steadman and Thrush (1994) that the green line is excited by energy transfer from the O2(A3Σu+, v≥6) molecules, and the inferred rate coefficient of this transfer is 1.5×10−11 cm3 s−1. The O2 bands at 762 nm and 1.27 μm are excited directly, by quenching of the Herzberg states, and by energy transfer from the O2(5Πg) state. Quenching of the O2 band at 762 nm excites the band at 1.27 μm as well. Effective yield of the O2(a1Δg) state in termolecular association on Venus and Mars is ∼0.7. Quantitative assessments of all these processes have been made. A possible reaction of O2(c1Σu−)+CO is a very minor branch of recombination of CO2 on Venus and Mars. Night airglow on Mars is calculated for typical conditions of the nighttime atmosphere. The calculated vertical intensity of the O2 band at 1.27 μm is 13 kR, far below the recently reported detections.  相似文献   

15.
Auroral ultraviolet spectra in the range 1200–3200 A have been obtained by the spectrometer onboard the OGO-4 satellite. Emissions of N2, H, O and N are readily identified. Atomic and molecular intensities are deduced from the comparison with a synthetic spectrum and compare reasonably well with some previous measurements and calculations. A feature at 2150 A is assigned to the (1-0) NO γ band. Taking into consideration the various excitation mechanisms of NO(A2σ) we propose that the energy transfer from N2 metastable molecules to oxygen accounts for the excitation of the NO γ bands. In particular, we suggest that the resonant reaction between O2 and highly metastable N2(W3Δ) molecules may be a major source of NO(A2σ).  相似文献   

16.
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   

17.
W-H. IP  D.A. Mendis 《Icarus》1976,28(3):389-400
  相似文献   

18.
Recently, modelers have expressed a concern that the currently known chemistry of atmospheric NOy is deficient. It is therefore necessary to explore possible sources and sinks of atmospheric NOx that may have been overlooked. In this context, it is noteworthy that the experimentally observed, four-center, Woodward-Hoffman forbidden, reaction 02(B 3Σ) + N2 → NO(X) + NO (X) is atmospherically significant. In the 20 to 30 km region NOx production from this reaction may potentially exceed the production from the “classical” N20 + O(1D) reaction, and may provide a new mechanism to couple the solar UV variability and stratospheric ozone. The avoidance of the non-conservation of the orbital symmetry via the production of one NO in the excited electronic state being endothermic, it appears that the interaction of 02(B 3Σ) with the adjoining 1Λ, 3Λ and 3Σu+ states might be responsible for the reaction. Experimental studies of the reaction as a function of the vibrational levels of the B-state, temperature and pressure are needed for reliable atmospheric applications of this reaction. At altitudes greater than about 50 km the production of NO from 02(B) begins to decrease rapidly. The NO production from 02 (A 3Σ++) + N2 → NO + NO reaction may become important here, if the reaction is confirmed by experiments. These new sources of NOx call for new sinks of this species. In the upper stratosphere and mesosphere the chemical acceleration of NO dissociation via the reactions of electronically and vibrationally excited NO with 02 may help. In the lower atmosphere there is a possibility of the annihilation of NO, N02pair leading to the recreation of a stable NN bond. This might happen if N203 from NO and N02 recombination may photodissociate as N20 + 02. Unfortunately the requirements are stringent, and only experiments can tell whether or not this mechanism operates in the atmosphere.  相似文献   

19.
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 Te = 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.  相似文献   

20.
High-resolution spectra of Venus and Mars at the NO fundamental band at 5.3 μm with resolving power ν/δν=76,000 were acquired using the TEXES spectrograph at NASA IRTF on Mauna Kea, Hawaii. The observed spectrum of Venus covered three NO lines of the P-branch. One of the lines is strongly contaminated, and the other two lines reveal NO in the lower atmosphere at a detection level of 9 sigma. A simple photochemical model for NO and N at 50-112 km was coupled with a radiative transfer code to simulate the observed equivalent widths of the NO and some CO2 lines. The derived NO mixing ratio is 5.5±1.5 ppb below 60 km and its flux is . Predissociation of NO at the (0-0) 191 nm and (1-0) 183 nm bands of the δ-system and the reaction with N are the only important loss processes for NO in the lower atmosphere of Venus. The photochemical impact of the measured NO abundance is significant and should be taken into account in photochemical modeling of the Venus atmosphere. Lightning is the only known source of NO in the lower atmosphere of Venus, and the detection of NO is a convincing and independent proof of lightning on Venus. The required flux of NO is corrected for the production of NO and N by the cosmic ray ionization and corresponds to the lightning energy deposition of . For a flash energy on Venus similar to that on the Earth (∼109 J), the global flashing rate is ∼90 s−1 and ∼6 km−2 y−1 which is in reasonable agreement with the existing optical observations. The observed spectrum of Mars covered three NO lines of the R-branch. Two of these lines are contaminated by CO2 lines, and the line at 1900.076 cm−1 is clean and shows some excess over the continuum. Some photochemical reactions may result in a significant excitation of NO (v=1) in the lowest 20 km on Mars. However, quenching of NO (v=1) by CO2 is very effective below 40 km. Excitation of NO (v=1) in the collisions with atomic oxygen is weak because of the low temperature in the martian atmosphere, and we do not see any explanation of a possible emission of NO at 5.3 μm. Therefore the data are treated as the lack of absorption with a 2 sigma upper limit of 1.7 ppb to the NO abundance in the lower atmosphere of Mars. This limit is above the predictions of photochemical models by a factor of 3.  相似文献   

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