Temperature Dependences for the Reactions of O- and O2- with O2(a1Δg) from 200 to 700 K

2008 
Rate constants and product ion distributions for the O- and O2- reactions with O2(a 1Δg) 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 1Δg) emission detection scheme with a chemical singlet oxygen generator. The rate constant for the O2- reaction is ∼7 × 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 rat...
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