Paramagnetic proton nuclear magnetic relaxation in the Ni²⁺hexa-aquo complex

Abstract

Abstract The nuclear magnetic relaxation of the protons in the Ni2+(H2O)6 complex is analysed using a previously developed formalism (Benetis et al. 1983, Molec. Phys., 48, 329) for the description of paramagnetic nuclear spin relaxation in systems with a complex electron spin relaxation. The nuclear spin relaxation can be described within the Redfield theory and the transverse relaxation rate is expressed in terms of a spectral density K 1, -1(ωI), which is the Fourier-Laplace transform of a complex correlation function. In the Ni2+(H2O) complex the electron spin relaxation is caused by the zero field splitting (ZFS) and to evaluate the correlation function it is necessary to specify the dynamics of the ZFS. Three models are considered for this motion: (i) modulation of the ZFS by quantized vibrations, (ii) a classical pseudo-rotation of the ZFS at constant amplitude and (iii) a classical motion of the ZFS in an harmonic potential governed by the Smoluchowski equation.