Interpretation of magnetic resonance data from water nuclei in heterogeneous systems

Abstract

Nuclear magnetic resonance (NMR) data from water nuclei (1H, 2H, and 17O) can provide much information about the state of water in heterogeneous systems. In the present work, we present a theoretical framework for the interpretation of such data and discuss the implications of the theory. Due to the local anisotropy in heterogeneous systems, it is necessary to consider two components of water motion: a fast anisotropic reorientation superposed on a more extensive slow motion. On the basis of the experimentally verified assumption that these motions occur on different time scales, we develop a ’’two-step’’ model of relaxation, showing that both motions may give important contributions to the relaxation. We derive a simple expression for the relevant correlation function, valid for isotropic systems. Anisotropic systems are also treated, making use of a new symmetry theorem for time correlation functions. The proof of this theorem is given in an Appendix. The magnitudes of the water 2H and 17O quadrupole coupling constants are estimated to 0.222 and 6.67 MHz, respectively. Results of ab initio quantum chemical calculations are presented, demonstrating the insensitivity of the water 17O field gradient to nearby ionic species. The possibilities and limitations of the NMR technique in answering the fundamental questions about water structure and dynamics in heterogeneous systems are discussed. We suggest a novel interpretation of the well-known invariance of the ratio of 1H and 2H splittings. Furthermore, we argue that the available NMR data are consistent with a short-ranged (≲2 molecular layers) perturbation of the water tumbling rate and anisotropy.