A Computational Study on Halogen/Halide Redox Mediators and Their Role in (1)O(2) Release in Aprotic Li–O(2) Batteries

[Image: see text] We present a computational study on the redox reactions of small clusters of Li superoxide and peroxide in the presence of halogen/halide redox mediators. The study is based on DFT calculations with a double hybrid functional and an implicit solvent model. It shows that iodine is less effective than bromine in the oxidation of Li(2)O(2) to oxygen. On the basis of our thermodynamic data, in solvents with a low dielectric constant, iodine does not spontaneously promote either the oxidation of Li(2)O(2) or the release of singlet oxygen, while bromine could spontaneously trigger both events. When a solvent with a large dielectric constant is used, both halogens appear to be able, at least on the basis of thermodynamics, to react spontaneously with the oxides, and the ensuing reaction sequence turned out to be strongly exoergic, thereby providing a route for the release of significant amounts of singlet oxygen. The role of spin–orbit coupling in providing a mechanism for singlet–triplet intersystem crossing has also been assessed.