O2(X³Σg⁻) and O2(a¹Δg) charge exchange with simple ions.

We present theory and experiments which describe charge transfer from the X³Σg⁻ and a(1)Δg states of molecular oxygen and atomic and molecular cations. Included in this work are new experimental results for O2(a(1)Δg) and the cations O(+), CO(+), Ar(+), and N2⁺, and new theory based on complete active space self-consistent field method calculations and an extended Langevin model to calculate rate constants for ground and excited O2 reacting with the atomic ions Ar(+), Kr(+), Xe(+), Cl(+), and Br(+). The T-shaped orientation of the (X - O2)(+) potential surface is used for the calculations, including all the low lying states up to the second singlet state of the oxygen molecule b¹Σ(g)⁺. The calculated rate constants for both O2(X³Σg⁻) and O2(a(1)Δg) show consistent trends with the experimental results, with a significant dependence of rate constant on charge transfer exothermicity that does not depend strongly on the nature of the cation. The comparisons with theory show that partners with exothermicities of about 1 eV have stronger interactions with O2, leading to larger Langevin radii, and also that more of the electronic states are attractive rather than repulsive, leading to larger rate constants. Rate constants for charge transfer involving O2(a(1)Δg) are similar to those for O2(X³Σg⁻) for a given exothermicity ignoring the electronic excitation of the O2(a(1)Δg) state. This means (and the electronic structure calculations support) that the ground and excited states of O2 have about the same attractive interactions with ions.

Temperature dependences for the reactions of O- and O2- with O2(a1Deltag) from 200 to 700 K.

Rate constants and product ion distributions for the O- and O2- reactions with O2(a 1Deltag) were measured as a function of temperature from 200 to 700 K. The measurements were made in a selected ion flow tube (SIFT) using a newly calibrated O2(a 1Deltag) emission detection scheme with a chemical singlet oxygen generator. The rate constant for the O2- reaction is approximately 7 x 10(-10) cm3 s-1 at all temperatures, approaching the Langevin collision rate constant. Electron detachment was the only product observed with O2-. The O- reaction shows a positive temperature dependence in the rate constant from 200 to 700 K. The product branching ratios show that almost all of the products at 200 K are electron detachment, with an increasing contribution from the slightly endothermic charge-transfer channel up to 700 K, accounting for 75% of the products at that temperature. The increase in the overall rate constant can be attributed to this increase in the contribution the endothermic channel. The charge-transfer product channel rate constant follows the Arrhenius form, and the detachment product channel rate constant is essentially independent of temperature with a value of approximately 6.1 x 10(-11) cm3 s-1.

Kinetics for the reactions of O- and O2- with O2(a1Deltag) measured in a selected ion flow tube at 300 K.

The kinetics of the reactions of O- and O2- with O2(a1Deltag) have been studied at 300 K in a selected ion flow tube (SIFT). The O2(a1Deltag) concentrations have been determined using emission at 1270 nm from the O2(a1Deltag, v=0-->X3Sigmag-, v=0) transition measured with an InGaAs detector calibrated against absolute spectrally dispersed emission measurements. The rate constants measured for O- and O2- are 1.1x10(-10) and 6.6x10(-10) cm3 s-1, respectively, with uncertainties of +/-35%. The O2- reaction only produces electrons and can be described as Penning detachment, while the O- reaction has been found to produce both O2- and e-. The O2- branching fraction has a lower limit of approximately 0.30. Comparison of the present results to previous measurements found in the literature provides a resolution to a previous discrepancy in the rate constant values.