E.P.R. studies of the structure, mobility and reactivity of CO ? 2 and CO ? 3 species adsorbed on MgO

Abstract
F+-centres trapped in u.v. irradiated MgO react with CO2 to yield CO 2 radicals. The mobility and the structure of the adsorbed CO 2 radicals depend on the reaction temperature. Besides the usual CO 2 radical a rotating CO 2 radical was observed, being more reactive towards N2O to give the CO 3 radical with g⊥= 2.014 and g∥= 2.006 which exhibited a flexional behaviour. It was converted into the more conventional CO 3 species rigidly held on the surface of MgO, and characterized by g∥≃ 2.018 and g⊥= 2.006. In the process of this conversion a mobile CO 3 radical could be detected, it exhibited an isotropic g-tensor at g= 2.012 due to motional averaging.

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