Abstract
A low-field theory for paramagnetic relaxation enhancement (PRE), appropriate for the outer-sphere relaxation, is presented for the electron spin quantum number S = 1, 3/2, 2, 5/2, 3 and 7/2. The theory is used to calculate the PRE at low magnetic field, as a function of the translational diffusion coefficient, for various values of the electron spin quantum number, for small and fairly large values of the static zero-field splitting (ZFS), and for a given set of parameters determining the electron spin relaxation. We have found earlier that the static ZFS has a profound influence on the electron spin relaxation; such effects are also evident in the present study. Comparisons are made with other existing models for the outer-sphere PRE, and significant differences are found for slowly diffusing systems with large ZFS. The theory is also used to obtain a novel interpretation of experimental data for an acetone solution of a Mn(III) complex.
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