Application of two-dimensional exchange nuclear magnetic resonance techniques for the study of incommensurate solids.

摘要

This dissertation includes a study of atomic dynamics in incommensurate systems by specialized nuclear magnetic resonance (NMR) techniques, such as two-dimensional (2D) exchange NMR, and Hahn spin-echo decay.; The atomic dynamics described by the diffusion-like motion of the modulation wave in incommensurate phases is one of the subjects of condensed matter physics that is not fully understood and has attracted a great deal of attention in recent years. Our Hahn spin-echo decay and 2D exchange and exchange-difference NMR experiments have contributed to understanding some of the aspects of this debated subject and have brought conclusive experimental evidence for the existence of the modulation wave diffusion in Rb₂ZnCl ₄ and BaNaNb₅O₁₅.; We performed 87Rb NMR and 35Cl nuclear quadrupole resonance (NQR) Hahn spin echo magnetization decay measurements in the incommensurate (I) phase of Rb₂ZnCl₄. From these measurements we obtained values for the diffusion coefficients for 87Rb NMR and 35Cl NQR and found them to be similar. This fact strongly supports the existence of modulation wave diffusion in the I phase, that should affect both Rb and Cl ions comparably.; We also used 87Rb 2D exchange-difference NMR to study atomic motions in the incommensurate (I) and paraelectric (P) phases, to elucidate the nature of the I-P transition. The P phase results are identified as normal modes arising from simultaneous reorientations of ZnCl₄ tetrahedra and corresponding Rb ions displacements between two sites. These normal modes freeze out in the I phase and change to the diffusion-like motion of the modulation wave.; This dissertation also includes a study of modulation wave dynamics in the I phase of barium sodium niobate (BSN) by 2D exchange NMR. The modulation wave diffusion has been previously inferred in BSN from a complementary experiment, the Hahn spin-echo decay. However, since this experiment cannot unambiguously distinguish between different types of motional mechanisms, the modulation wave diffusion interpretation of the Hahn echo experimental results could still be under question. Our 93Nb 2D exchange NMR data provide additional strong evidence for the existence of progressive diffusion-like motion of the modulation wave and rules out a two-site jump model in BSN.