Low-lying plasma layers have been observed sporadically in the Martian atmosphere by radio occultation measurements from spacecraft such as the Mars Express Orbiter and the Mars Global Surveyor. These layers are just a few km wide, and tend to occur around 90 km. It has been proposed that the layers consist of metallic ions, for two reasons: they occur in the aerobraking region of the planet where meteoroids ablate; and they resemble sporadic E layers in the terrestrial atmosphere which are known to be composed principally of Fe+ and Mg+ ions. This paper addresses the problem of how metallic ions can persist in a CO2-rich atmosphere, where the ions should be neutralized rapidly by formation of metal-CO2 cluster ions followed by dissociative electron recombination. Laboratory studies using the pulsed laser photolysis/laser induced fluorescence and flow tube/mass spectrometer techniques were used to measure the following rate coefficients: k (Mg+ + CO2 (+ CO2) --> Mg+ x CO2, 190-403 K) = (5.3 +/- 0.7) x 10(-29) (T/300 K)(-1.86 +/- 0.03) cm6 molecule --> 2 s(-1); k(Mg+ x CO2 + O2 --> MgO2(+) + CO2, 297 K) = (2.2 +/- 0.8) x 10(-11) cm3 molecule(-1) s(-1); k(MgO2(+) + O --> MgO(+) + O2, 297 K) = (6.5 +/- 1.8) x 10(-10) cm3 molecule(-1) s(-1); and k(MgO(+) + O --> Mg(+) + O2, 297 K) = (5.9 +/- 2.4) x 10(-10) cm3 molecule(-1) s(-1). A model of magnesium and iron chemistry in the Martian atmosphere was then constructed, which includes meteoric differential ablation rates calculated with the Leeds CABMOD model, photo-ionization, and gas-phase ion-molecule and neutral chemistry. The model shows that nearly all the metallic ions between 70 and 110 km should be Mg+, because the reactions of MgO2+ and MgO+ with atomic O are fast enough to prevent these molecular ions undergoing dissociative electron recombination (unlike the analogous Fe species). There are enough Mg+ ions to form sporadic layers of the observed plasma density, and the layers can have a lifetime against neutralization in excess of 20 h.

This paper describes the kinetic study of a number of gas-phase reactions involving neutral Mg-containing species, which are important for the chemistry of meteor-ablated magnesium in the upper mesosphere/lower thermosphere region. The study is motivated by the very recent observation of the global atomic Mg layer around 90 km, using satellite-born UV-visible spectroscopy. In the laboratory, Mg atoms were produced thermally in the upstream section of a fast flow tube and then converted to the molecular species MgO, MgO(2), OMgO(2), and MgCO(3) by the addition of appropriate reagents. Atomic O was added further downstream, and Mg was detected at the downstream end of the flow tube by laser-induced fluorescence. The following rate coefficients were determined at 300 K: k(MgO + O → Mg + O(2)) = (6.2 ± 1.1) × 10(-10); k(MgO(2) + O → MgO + O(2)) = (8.4 ± 2.8) × 10(-11); k(MgCO(3) + O → MgO(2) + CO(2)) ≥ 4.9 × 10(-12); and k(MgO + CO → Mg + CO(2)) = (1.1 ± 0.3) × 10(-11) cm(3) molecule(-1) s(-1). Electronic structure calculations of the relevant potential energy surfaces combined with RRKM theory were performed to interpret the experimental results and also to explore the likely reaction pathways that convert MgCO(3) and OMgO(2) into long-lived reservoir species such as Mg(OH)(2). Although no reaction was observed in the laboratory between OMgO(2) and O, this is most likely due to the rapid recombination of O(2) with the product MgO(2) to form the relatively stable O(2)MgO(2). Indeed, one significant finding is the role of O(2) in the mesosphere, where it initiates holding cycles by recombining with radical species such as MgO(2) and MgOH. A new atmospheric model was then constructed which combines these results together with recent work on magnesium ion-molecule chemistry. The model is able to reproduce satisfactorily some of the key features of the Mg and Mg(+) layers, including the heights of the layers, the seasonal variations of their column abundances, and the unusually large Mg(+)/Mg ratio.

Reactions between Mg(+) and O(3), O(2), N(2), CO(2) and N(2)O were studied using the pulsed laser photo-dissociation at 193 nm of Mg(C(5)H(7)O(2))(2) vapour, followed by time-resolved laser-induced fluorescence of Mg(+) at 279.6 nm (Mg(+)(3(2)P(3/2)-3(2)S(1/2))). The rate coefficient for the reaction Mg(+) + O(3) is at the Langevin capture rate coefficient and independent of temperature, k(190-340 K) = (1.17 ± 0.19) × 10(-9) cm(3) molecule(-1) s(-1) (1σ error). The reaction MgO(+) + O(3) is also fast, k(295 K) = (8.5 ± 1.5) × 10(-10) cm(3) molecule(-1) s(-1), and produces Mg(+) + 2O(2) with a branching ratio of (0.35 ± 0.21), the major channel forming MgO(2)(+) + O(2). Rate data for Mg(+) recombination reactions yielded the following low-pressure limiting rate coefficients: k(Mg(+) + N(2)) = 2.7 × 10(-31) (T/300 K)(-1.88); k(Mg(+) + O(2)) = 4.1 × 10(-31) (T/300 K)(-1.65); k(Mg(+) + CO(2)) = 7.3 × 10(-30) (T/300 K)(-1.59); k(Mg(+) + N(2)O) = 1.9 × 10(-30) (T/300 K)(-2.51) cm(6) molecule(-2) s(-1), with 1σ errors of ±15%. Reactions involving molecular Mg-containing ions were then studied at 295 K by the pulsed laser ablation of a magnesite target in a fast flow tube, with mass spectrometric detection. Rate coefficients for the following ligand-switching reactions were measured: k(Mg(+)·CO(2) + H(2)O → Mg(+)·H(2)O + CO(2)) = (5.1 ± 0.9) × 10(-11); k(MgO(2)(+) + H(2)O → Mg(+)·H(2)O + O(2)) = (1.9 ± 0.6) × 10(-11); k(Mg(+)·N(2) + O(2)→ Mg(+)·O(2) + N(2)) = (3.5 ± 1.5) × 10(-12) cm(3) molecule(-1) s(-1). Low-pressure limiting rate coefficients were obtained for the following recombination reactions in He: k(MgO(2)(+) + O(2)) = 9.0 × 10(-30) (T/300 K)(-3.80); k(Mg(+)·CO(2) + CO(2)) = 2.3 × 10(-29) (T/300 K)(-5.08); k(Mg(+)·H(2)O + H(2)O) = 3.0 × 10(-28) (T/300 K)(-3.96); k(MgO(2)(+) + N(2)) = 4.7 × 10(-30) (T/300 K)(-3.75); k(MgO(2)(+) + CO(2)) = 6.6 × 10(-29) (T/300 K)(-4.18); k(Mg(+)·H(2)O + O(2)) = 1.2 × 10(-27) (T/300 K)(-4.13) cm(6) molecule(-2) s(-1). The implications of these results for magnesium ion chemistry in the atmosphere are discussed.

The first excited electronic state of molecular oxygen, O 2 (a 1 g ), is formed in the upper atmosphere by the photolysis of O 3 . Its lifetime is over 70 min above 75 km, so that during the day its concentration is about 30 times greater than that of O 3 . In order to explore its potential reactivity with atmospheric constituents produced by meteoric ablation, the reactions of Mg, Fe, and Ca with O 2 (a) were studied in a fast flow tube, where the metal atoms were produced either by thermal evaporation (Ca and Mg) or by pulsed laser ablation of a metal target (Fe), and detected by laser induced fluorescence spectroscopy. O 2 (a) was produced by bubbling a flow of Cl 2 through chilled alkaline H 2 O 2 , and its absolute concentration determined from its optical emission at 1270 nm (O 2 (a 1The following results were obtained at 296The total uncertainty in these rate coefficients, which mostly arises from the systematic uncertainty in the O 2 (a) concentration, is estimated to be ±40%. Mg + O 2 (a) occurs exclusively by association on the singlet surface, producing MgO 2 ( 1 A 1 ), with a pressure dependent rate coefficient. Fe + O 2 (a), on the other hand, shows pressure independent kinetics. FeO + O is produced with a probability of only ∼0.1%. There is no evidence for an association complex, suggesting that this reaction proceeds mostly by nearresonant electronic energy transfer to Fe(a 5 F) + O 2 (X). The reaction of Ca + O 2 (a) occurs in an intermediate regime with two competing pressure dependent channels: (1) a recombination to produce CaO 2 ( 1 A 1 ), and (2) a singlet/triplet non-adiabatic hopping channel leading to CaO + O( 3 P). In order to interpret the Ca + O 2 (a) results, we utilized density functional theory along with multireference and explicitly correlated CCSD(T)-F12 electronic structure calculations to examine the lowest lying singlet and triplet surfaces. In addition to mapping stationary points, we used a genetic algorithm to locate minimum energy crossing points between the two surfaces. Simulations of the Ca + O 2 (a) kinetics were then carried out using a combination of both standard and non-adiabatic Rice-Ramsperger-Kassel-Marcus (RRKM) theory implemented within a weak collision, multiwell master equation model. In terms of atmospheric significance, only in the case of Ca does reaction with O 2 (a) compete with O 3 during the daytime between 85 and 110 km.

A laser flash photolysis technique and quasi-classical trajectory (QCT) calculations have been used to determine the rate coefficients for the title process. The experimental high-pressure-limiting rate coefficient is 7.0 x 10(-11) cm(3) s(-1) at T = 300 K, which compares with the computed QCT value for the Mg(+) + H(2)O capture rate of 2.75 +/- 0.08 x 10(-9) cm(3) s(-1) at the same temperature. The 39-fold difference between the experimental and simulation results is explained by further QCT calculations for the He + Mg(+).H(2)O* collision process. In particular, our simulation results indicate that collision-induced dissociation (CID) of the Mg(+).H(2)O* excited adduct is very likely compared with collisional stabilization (CS), which is an order of magnitude less likely. Including the relative rates of CID and CS in the calculation and assuming that those Mg(+).H(2)O* complexes that perform only one inner turning point in the dissociation coordinate are unlikely to be stabilized by CS, the computed rate coefficient compares well with the high-pressure experimental value.