DOE OSTI2012
The first excited electronic state of molecular oxygen, O{sub 2}(a{sup 1}{Delta}{sub g}), is formed in the upper atmosphere by the photolysis of O{sub 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{sub 3}. In order to explore its potential reactivity with atmospheric constituents produced by meteoric ablation, the reactions of Mg, Fe, and Ca with O{sub 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{sub 2}(a) was produced by bubbling a flow of Cl{sub 2} through chilled alkaline H{sub 2}O{sub 2}, and its absolute concentration determined from its optical emission at 1270 nm (O{sub 2}(a{sup 1}{Delta}{sub g}- X{sup 3}{Sigma}{sub g}{sup -}). The following results were obtained at 296 K: k(Mg + O{sub 2}(a) + N{sub 2}{yields} MgO{sub 2}+ N{sub 2}) = (1.8 {+-} 0.2) Multiplication-Sign 10{sup -30} cm{sup 6} molecule{sup -2} s{sup -1}; k(Fe + O{sub 2}(a) {yields} FeO + O) = (1.1 {+-} 0.1) Multiplication-Sign 10{sup -13} cm{sup 3} molecule{sup -1} s{sup -1}; k(Ca + O{sub 2}(a) + N{sub 2}{yields} CaO{sub 2}+ N{sub 2}) = (2.9 {+-} 0.2) Multiplication-Sign 10{sup -28} cm{sup 6} molecule{sup -2} s{sup -1}; and k(Ca + O{sub 2}(a) {yields} CaO + O) = (2.7 {+-} 1.0) Multiplication-Sign 10{sup -12} cm{sup 3} molecule{sup -1} s{sup -1}. The total uncertainty in these rate coefficients, which mostly arises from the systematic uncertainty in the O{sub 2}(a) concentration, is estimated to be {+-}40%. Mg + O{sub 2}(a) occurs exclusively by association on the singlet surface, producing MgO{sub 2}({sup 1}A{sub 1}), with a pressure dependent rate coefficient. Fe + O{sub 2}(a), on the other hand, shows pressure independent kinetics. FeO + O is produced with a probability of only {approx}0.1%. There is no evidence for an association complex, suggesting that this reaction proceeds mostly by near-resonant electronic energy transfer to Fe(a{sup 5}F) + O{sub 2}(X). The reaction of Ca + O{sub 2}(a) occurs in an intermediate regime with two competing pressure dependent channels: (1) a recombination to produce CaO{sub 2}({sup 1}A{sub 1}), and (2) a singlet/triplet non-adiabatic hopping channel leading to CaO + O({sup 3}P). In order to interpret the Ca + O{sub 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{sub 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{sub 2}(a) compete with O{sub 3} during the daytime between 85 and 110 km.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗