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The Nuclear Overhauser Effect aims to provide a unified treatment of both the theory and applications of the NOE that would be accessible to the chemist who is not a specialist in NMR, but who would nevertheless like to use the NOE to solve problems in his own area of interest. Assuming only that the reader has a typical chemist's working knowledge of NMR, an attempt is made to present the results in each section in a sufficiently simple form so that little mathematical sophistication will be required to apply them with understanding. This book comprises eight chapters, and begins with a focus on nuclear spin-lattice relaxation. The following chapters then discuss mechanisms of spin-lattice relaxation; the nuclear overhauser effect in rigid molecules; the effects of internal motions; experimental methods; transient methods; the effects of chemical exchange; and applications of the nuclear overhauser effect, with a review of available literature. This book will be of interest to practitioners in the fields of chemistry and physics.
The idea that a long-lived form of spin order, namely singlet order, can be prepared from nuclear spin magnetisation first emerged in 2004. The unusual properties of singlet order–its long lifetime and the fact that it is NMR silent but interconvertible into other forms of NMR active order—make it a ‘smart tag’ that can be used to store information for a long time or through distant space points. It is not unexpected then, that since its first appearance, this idea has caught the attention of research groups interested in exploiting this form of order in different fields of research spanning from biology to materials science and from hyperpolarisation to quantum computing. This first book on the subject gives a thorough description of the various aspects that affect the development of the topic and details the interdisciplinary applications. The book starts with a section dedicated to the basic theories of long-lived spin order and then proceeds with a description of the state-of-the-art experimental techniques developed to manipulate singlet order. It then concludes by covering the generalization of the concept of singlet order by introducing and discussing other forms of long-lived spin order.
Part I of this dissertation is a study of the magnetic isotope effect, and results are presented for the separation of 13C and 12C isotopes. Two models are included in the theoretical treatment of the effect. In the first model the spin states evolve quantum mechanically, and geminate recombination is calculated by numerically integrating the collision probability times the probability the radical pair is in a singlet state. In the second model the intersystem crossing is treated via first-order rate constants which are average values of the hyperfine couplings. Using these rate constants and hydrodynamic diffusion equations, an analytical solution, which accounts for all collisions, is obtained for the geminate recombination. The two reactions studied are photolysis of benzophenone and toluene and the photolytic decomposition of dibenzylketone (1,3-diphenyl-2-propanone). No magnetic isotope effect was observed in the benzophenone reaction. 13C enrichment was observed for the dibenzylketone reaction, and this enrichment was substantially enhanced at intermediate viscosities and low temperatures. Part II of this dissertation is a presentation of theory and results for the use of Zeeman spin-lattice relaxation as a probe of methyl group rotation in the solid state. Experimental results are presented for the time and angular dependences of rotational polarization, the methyl group magnetic moment, and methyl-methyl steric interactions. The compounds studied are 2,6-dimethylphenol, methyl iodide, 1,4,5,8-tetramethylanthracene, 1,4,5,8-tetramethylnaphthalene, 1,2,4,5-tetramethylbenzene, and 2,3-dimethylmaleicanhydride.
Nuclear magnetic resonance (NMR) is widely used across many fields of science because of the rich data it produces, and some of the most valuable data come from studies of nuclear spin relaxation in solution. The first edition of this book, published more than a decade ago, provided an accessible and cohesive treatment of the field. The present second edition is a significant update, covering important new developments in recent years. Collecting relaxation theory, experimental techniques, and illustrative applications into a single volume, this book clarifies the nature of the phenomenon, shows how to study it and explains why such studies are worthwhile. Coverage ranges from basic to rigorous theory and from simple to sophisticated experimental methods. Topics include cross-relaxation, multispin phenomena, relaxation studies of molecular dynamics and structure and special topics such as relaxation in systems with quadrupolar nuclei, in paramagnetic systems and in long-living spin states. Avoiding overly demanding mathematics, the authors explain spin relaxation in a manner that anyone with a familiarity with NMR can follow. The focus is on illustrating and explaining the physical nature of relaxation phenomena. Nuclear Spin Relaxation in Liquids: Theory, Experiments and Applications, 2nd edition, provides useful supplementary reading for graduate students and is a valuable reference for NMR spectroscopists, whether in chemistry, physics or biochemistry.
Nuclear magnetic resonance (NMR) is widely used across many fields because of the rich data it produces, and some of the most valuable data come from the study of nuclear spin relaxation in solution. While described to varying degrees in all major NMR books, spin relaxation is often perceived as a difficult, if not obscure, topic, and an accessible, cohesive treatment has been nearly impossible to find. Collecting relaxation theory, experimental techniques, and illustrative applications into a single volume, this book clarifies the nature of the phenomenon, shows how to study it, and explains why such studies are worthwhile. Coverage ranges from basic to rigorous theory and from simple to sophisticated experimental methods, and the level of detail is somewhat greater than most other NMR texts. Topics include cross-relaxation, multispin phenomena, relaxation studies of molecular dynamics and structure, and special topics such as relaxation in systems with quadrupolar nuclei and paramagnetic systems. Avoiding overly demanding mathematics, the authors explain relaxation in a manner that anyone with a basic familiarity with NMR can follow, regardless of their specialty. The focus is on illustrating and explaining the physical nature of the phenomena, rather than the intricate details. Nuclear Spin Relaxation in Liquids: Theory, Experiments, and Applications forms useful supplementary reading for graduate students and a valuable desk reference for NMR spectroscopists, whether in chemistry, physics, chemical physics, or biochemistry.
From the initial observation of proton magnetic resonance in water and in paraffin, the discipline of nuclear magnetic resonance has seen unparalleled growth as an analytical method. Modern NMR spectroscopy is a highly developed, yet still evolving, subject which finds application in chemistry, biology, medicine, materials science and geology. In this book, emphasis is on the more recently developed methods of solution-state NMR applicable to chemical research, which are chosen for their wide applicability and robustness. These have, in many cases, already become established techniques in NMR laboratories, in both academic and industrial establishments. A considerable amount of information and guidance is given on the implementation and execution of the techniques described in this book.
Readership: Graduate students, researchers and industrialists in chemistry, physics and biology.