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Coherence transfer and electron T1-, T2-relaxation in nitroxide spin labels.

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Marsh,  D.
Department of NMR Based Structural Biology, MPI for biophysical chemistry, Max Planck Society;

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Marsh, D. (2017). Coherence transfer and electron T1-, T2-relaxation in nitroxide spin labels. Journal of Magnetic Resonance, 277, 86-94. doi:10.1016/j.jmr.2017.02.006.


Cite as: http://hdl.handle.net/11858/00-001M-0000-002D-07FB-E
Abstract
Abragam's double-commutator spin operator method is used to analyse: 1) electron coherence transfer by intermolecular dipolar interaction between spin-label radicals, and 2) longitudinal and transverse electron spin relaxation by rotational modulation of the Zeeman and nitrogen-hyperfine anisotropies of isolated nitroxide spin labels. Results compatible with earlier treatments by Redfield theory are obtained without specifically evaluating matrix elements. Extension to single-transition operators for isolated nitroxides predicts electron coherence transfer by pseudosecular electron-nuclear dipolar interaction, in the absence of intermolecular dipolar coupling. This explains earlier experimental findings that coherence transfer (specifically dispersion-like distortion of the EPR absorption line shape) does not extrapolate to zero at low concentrations of nitroxide spin labels.