Abstract
A quantitative study of the chemically induced dynamic electron polarization (CIDEP) spectra of acetone and deuterated acetone ketyl radicals in i-propanol over a wide temperature range has been done to understand the properties of the radical pairs in solution, e.g., the interactions between the radicals, the diffusional and rotational motions of the radicals of the geminate radical pairs, and the microscopic solvent structure. The spin polarization of the separated radical is analyzed in terms of the stochastic-Liouville equation. It is shown that the observed polarization cannot be explained on the basis of the normal diffusion of the radicals in the pair. The modified diffusion models which presuppose slow diffusion of the radicals in a microscopic solvent structure can account for the observed polarization. The radical pair electron paramagnetic resonance (EPR) spectra observed at very low temperatures (<∼−70 °C) are explained by assuming that a considerable fraction of the radicals are held together in solvent structures whose lifetimes are a few microseconds. From the comparison with other alcohol and amine systems, we conclude that the observation of the radical pair EPR spectra is characteristic of alcohol solutions at very low temperatures.
Published Version
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