Abstract
The results of a room temperature ENDOR investigation of the secondary radicals formed after X-irradiation in a single crystal of α-calcium formate are reported and discussed. 39 different proton hyperfine tensors have been determined, belonging to magnetically or structurally different radicals. The hyperfine tensors are typical of α-protons in π-radicals, with a spin density ρc = 0·75 on the central carbon atoms. The radicals are identified therefore -O-ĊH-O-CO2 - in twelve slightly different conformations. The mechanisms giving rise to the reactions of primary σ-radicals CO2 - with the neighbouring undamaged molecules through cooperative rotations around the Ca-O bonds are discussed. It is shown that the experimentally determined C-H directions are very well reproduced by rotations of the formate groups around a Ca-O bond.
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