A spin statistical factor in electron transfer to oxygen molecules

Abstract

The oxygen molecule in its ground triplet state (³O₂) is a strong electron acceptor. Electron transfer to ³O₂ to form a superoxide anion is an important elementary step in many chemical and biological processes. If this transfer occurs from a spin 1/2 paramagnetic particle where the total spin of the reactants is equal to 3/2, the reaction is spin-forbidden. In liquids, the significant dipole-dipole electron spin interaction in ³O₂ is supposed to mix the non-reactive quartet and reactive doublet states at a time scale of ∼10 ps, thus avoiding the barrier. To elucidate the role of spin effects in the electron transfer to ³O₂, we studied this reaction over a range of more than three orders of magnitude of the relative diffusion coefficient (D) of the reactants. It was found that spin effects during electron transfer to ³O₂ become insignificant when D < 10^-9 m² s^-1. In the range of intermediate D values (10^-9 m² s^-1 < D < 10^-8 m² s^-1) - which corresponds to some reactions of oxygen with small radicals in aqueous solutions - the effective spin factor decreases with increasing D value. If D > 10^-8 m² s^-1, the electron transfer is spin-selective with the spin factor of 1/3 as determined by the spin statistics. At such D values, the reaction encounter time may exceed the expected quartet-doublet mixing time by almost an order of magnitude. The reduced rate of quartet-doublet transitions within the encounter complex in the reaction with ³O₂ has been explained by the spin-exchange interaction and chemical Zeno effect.