Journal of Physical Chemistry p. 2275 - 2284 (1984)
Update date:2022-08-30
Topics:
Drift, E. van der
Rousseeuw, B. A. C.
Smidt, J.
The spin relaxation of perdeuterated 2,2,6,6-tetramethyl-4-piperidone-N-oxyl (PDT) in various solvents was studied via EPR line width and saturation and ELDOR.Saturation and ELDOR results are incompatible with the line-width result when the latter are analyzed in the standard manner: rotational diffusion (RD) with temperature invariance of the anisotropy factor N and of the non-Debye parameter ε in the nonsecular spectral densities j(ω0).In a more general approach, first all relevant intramolecular relaxation terms are obtained independently from the combined T2, T1, and ELDOR data.Further analysis of these terms suggests that, in general, the rotational relaxation of PDT may arise from rotational diffusion (RD) and a slowly relaxing local structure mechanism (SRLS).Separation of RD and SRLS contributions seems possible via the electron spin relaxation rate, more particularly via the spin-rotational interaction part WeSR.This is most clearly shown by the results on PDT in methylcyclohexane (MCH) and in the isotropic phase of the liquid crystalline solvent 4'-n-octyl-4-cyanobiphenyl (8CB).Particularly, by virtue of the results on 8CB the combined T2-T1-ELDOR method seems promising in spin label/spin probe research on ordering media by its option to yield directly the ordering dynamics of the nearby environment.
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