Theory of intramolecular spin relaxation by translational diffusion in locally ordered fluids

Abstract

In locally ordered fluids, such as macromolecular solutions, clays and lyotropic liquid crystals, nuclear spin relaxation can be induced by modulation, through translational diffusion of the fluid molecules, of the magnitude and orientation of the residual intramolecular spin-lattice coupling tensor, which is only partially averaged by local molecular motions near an interface. A theory of spin relaxation in locally ordered fluids bounded by planar interfaces is developed, with special emphasis on effects of translational diffusion. The theory is based on a continuous diffusion model (CDM) which, in contrast to the commonly adopted discrete exchange model (DEM), treats equilibrium and time-dependent distribution functions in a self-consistent way. A striking feature of translational diffusion in heterogeneous systems is the abundance of reencounters with previously visited interfacial regions. It is demonstrated that these diffusional reencounters, which are inherent in the CDM theory, may lead to a relaxation behaviour which is qualitatively different from that predicted by the DEM theory. Furthermore, it is seen that the widespread concept of intrinsic relaxation rate (associated with a spatial region) and the fast/slow exchange classification are not generally valid. The formal framework of the CDM theory allows molecular interactions of any complexity to be introduced. In this paper a mean-field model based on the nonlinear Poisson-Boltzmann equation is used to obtain analytic expressions for the spectral density functions that determine the relaxation behaviour in the presence and in the absence of spectral line splittings.