Abstract
The nitroxylfree radicals, also known as nitroxide or aminoxyl radicals, are convenient, spectroscopically-active probes for many physicochemical studies. They have long been used to study the spatial distribution of paramagnetic centers in solids using PELDOR or DEER spectroscopy. The spatial distribution function \(F(r)\) between radicals can be determined from their distance-dependent dipolar interactions. The detailed spatial distribution of reactive species, particularly radicals or ion-radicals, often determines the kinetics of their reactions in solids. Nitroxyl radicals have been widely used for pulsed EPR experimental studies of magnetic relaxation processes, such as spectral and instantaneous diffusion, cross-relaxation, and spin-lattice relaxation. Their well-established chemical structure and stability make nitroxyls convenient, spectroscopically-active probes for many physicochemical studies. One area in which nitroxyls have been employed concerns the spatial distribution of paramagnetic centers in solids. The detailed spatial distribution of reactive species, particularly radicals or ion-radicals, often determines the kinetics of their reactions in solids. The spatial distribution function \(F(r)\) between radicals can be determined from their distance-dependent dipolar interactions using, e.g., ESE (Salikhov et al in Electron spin echo and its applications. Nauka, Novosibirsk, 1976 [1]; Salikhov and Tsvetkov in Time domain electron spin resonance. Wiley Interscience, New York, pp 232–277, 1977 [2]) or PELDOR techniques. In this chapter, we describe a few examples of the variety of spatial distributions that have been examined by PELDOR methods. Studies at X-band using nitroxyls and nitroxyl-labeled compounds were chosen to emphasize the distance distributions and to minimize complications from changes in mw frequency or spin properties at high frequency.
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