The first excited electronic state of molecular oxygen, O2(a1Δg), is formed in the upper atmosphere by the photolysis of O3. Its lifetime is over 70 min above 75 km, so that during the day its concentration is about 30 times greater than that of O3. In order to explore its potential reactivity with atmospheric constituents produced by meteoric ablation, the reactions of Mg, Fe, and Ca with O2(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. O2(a) was produced by bubbling a flow of Cl2 through chilled alkaline H2O2, and its absolute concentration determined from its optical emission at 1270 nm (O2(a1Δg<br> X3Σg −). The following results were obtained at 296 K: k(Mg + O2(a) + N2 → MgO2 + N2) = (1.8 ± 0.2) × 10−30 cm6 molecule−2 s−1; k(Fe + O2(a) → FeO + O) = (1.1 ± 0.1) × 10−13 cm3 molecule−1 s<br>1; k(Ca + O2(a) + N2 → CaO2 + N2) = (2.9 ± 0.2) × 10−28 cm6 molecule−2 s−1; and k(Ca + O2(a) → CaO + O) = (2.7 ± 1.0) × 10−12 cm3 molecule−1 s<br>1. The total uncertainty in these rate coefficients, which mostly arises from the systematic uncertainty in the O2(a) concentration, is estimated to be ±40%. Mg + O2(a) occurs exclusively by association on the singlet surface, producing MgO2(1A1), with a pressure dependent rate coefficient. Fe + O2(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 near-resonant electronic energy transfer to Fe(a5F) + O2(X). The reaction of Ca + O2(a) occurs in an intermediate regime with two competing pressure dependent channels: (1) a recombination to produce CaO2(1A1), and (2) a singlet/triplet non-adiabatic hopping channel leading to CaO + O(3P). In order to interpret the Ca + O2(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 + O2(a) kinetics were then carried out using a combination of both standard and non-adiabatic Rice<br>Ramsperger<br>Kassel<br>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 O2(a) compete with O3 during the daytime between 85 and 110 km.