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EPR of Free Radicals in Solids pp 95–152Cite as

Dynamical Effects in CW and Pulsed EPR

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Part of the book series: Progress in Theoretical Chemistry and Physics ((PTCP,volume 10))

Abstract

Typical molecular processes with EPR accessible dynamical parameters are catalogued and evaluation of their timescales according to the different EPR methods used for this purpose is described. The detection and description of the dynamics of small cyclic radicals and related nitroxide labels in solids and the connection to the structural parameters are given. Both fast-motion averaging and the method of lincshapc modification duc to chemical exchange are outlined. Some usually overlooked anomalies concerning the activation parameters of the thermally activated rotary motion and their relation to the microscopic variables of the spin-motion system are discussed. The definition of the thermodynamic limits differentiating diffusional motion from quantum motion and the particular ways of the couplings of these motions to the spin system are exemplified. Several experiments manifesting their difference, such as comparison of EPR spectra for classical and for tunnelling rotors, as well as severely distorted EPR spectra including totally quenched (stopped) methyl-type rotors are reviewed and explained. Spin-lattice relaxation and broadening are discussed for fast and slow motions in solids and the characterization of the dynamics according to the effects of motion on the ESE decay are considered in the framework of pulsed EPR. Finally, some standard biological applications in determining the timescales and the motional pattern of disordered matter at the molecular level are described with emphasis to the modern pulsed EPR techniques and some relevant recent developments.

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  1. Department of biological Chemistry, School of Medicine, University of Ioannina, 451 10, Greece

    Nikolas P. Benetis

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  1. Nikolas P. Benetis
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Editors and Affiliations

  1. Department of Physics and Measurement Technology, Linköping University, S-581 83, Linköping, Sweden

    Anders Lund

  2. Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, 739-8527, Higashi-Hiroshima, Japan

    Masaru Shiotani

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Benetis, N.P. (2003). Dynamical Effects in CW and Pulsed EPR. In: Lund, A., Shiotani, M. (eds) EPR of Free Radicals in Solids. Progress in Theoretical Chemistry and Physics, vol 10. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-5166-6_3

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