The role of anisotropic rotation for electron spin resonance lineshape and nuclear magnetic relaxation dispersion proles for paramagnetic molecules with electron spin quantum number S ≥ 1 is discussed. The ESR spectra and nuclear magnetic relaxation dispersion proles are calculated by means of an approach based on the stochastic Liouville equation and referred to in the literature as Swedish slow motion theory. This description is valid for arbitrary motional conditions and interaction strengths. Molecular tumbling inuences the ESR spectra by modulating zero eld splitting interactions. The nuclear spin relaxation is aected by the rotational motion in a twofold way: via the electron spin dynamics and as a direct source of modulations of the electron-nuclear dipoledipole interactions. For coinciding principal axes systems of the permanent (residual, static) zero eld splitting and rotational tensors the ESR lineshape is not aected by rotational anisotropy. Rotational anisotropy is important for nuclear relaxation as it is inuenced by molecular rotation not only via the electron spin dynamics, but also directly by modulations of the electron spinnuclear spin dipoledipole interaction (when the dipoledipole and zero eld splitting frames do not coincide). The anisotropy eects depend strongly on the relative orientation of the dipoledipole and permanent zero eld splitting axes. Nevertheless, a dierent scenario is also possible. When the diusion axis coincides with the dipoledipole axis (but not with the principal axis system of the permanent zero eld splitting), the nuclear spin relaxation as well as the ESR lineshape, become sensitive to the rotational anisotropy. The possible dependence of the ESR lineshape and nuclear spin relaxation on the rotational anisotropy should be carefully considered when attempting a joint analysis of ESR and nuclear magnetic relaxation dispersion results for paramagnetic molecules.
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