High Resolution NMR

Theory and Chemical Applications

2nd Edition - May 28, 1980
Author: Edwin D. Becker
Language: English
eBook ISBN:
9 7 8 - 0 - 3 2 3 - 1 6 1 8 5 - 5

High Resolution NMR: Theory and Chemical Applications discusses the principles and theory of nuclear magnetic resonance and how this concept is used in the chemical sciences. This… Read more

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High Resolution NMR: Theory and Chemical Applications discusses the principles and theory of nuclear magnetic resonance and how this concept is used in the chemical sciences. This book is written at an intermediate level, with mathematics used to augment verbal descriptions of the phenomena. This text pays attention to developing and interrelating four approaches – the steady state energy levels, the rotating vector picture, the density matrix, and the product operator formalism. The style of this book is based on the assumption that the reader has an acquaintance with the general principles of quantum mechanics, but no extensive background in quantum theory or proficiency in mathematics is required. This book begins with a description of the basic physics, together with a brief account of the historical development of the field. It looks at the study of NMR in liquids, including high resolution NMR in the solid state and the principles of NMR imaging and localized spectroscopy. This book is intended to assist chemistry graduate students, advanced undergraduate students, or researchers to understand NMR at a fundamental level. This text also provides illustrations of the applications of NMR to the determination of the structure of small organic molecules and macromolecules, including proteins.

Preface to Second Edition

Preface to First Edition

Acknowledgments

1. Introduction

1.1 Historical

1.2 High Resolution NMR

2. The Theory of NMR

2.1 Nuclear Spin and Magnetic Moment

2.2 Classical Mechanical Description of NMR

2.3 Quantum Mechanical Description of NMR

2.4 Effect of the Boltzmann Distribution

2.5 Spin-Lattice Relaxation

2.6 Line Widths

2.7 Saturation

2.8 Macroscopic Magnetization

2.9 The Bloch Equations: Nuclear Induction

2.10 The Rotating Frame of Reference

2.11 Adiabatic Passage; Ringing

Problems

3. Instrumentation and Techniques

3.1 Basic NMR Apparatus

3.2 Requirements for High Resolution NMR

3.3 Modulation and Phase Sensitive Detection

3.4 Field/Frequency Control

3.5 Signal/Noise and Size of Sample

3.6 Fourier Transform Methods

3.7 Intensity Measurements

3.8 References

3.9 Magnetic Susceptibility Measurements

3.10 Frequency Calibration

3.11 Control of Sample Temperature

3.12 Useful Solvents

3.13 Sampling Techniques

3.14 Micro Techniques

Problems

4. Chemical Shifts

4.1 The Origin of Chemical Shifts

4.2 Reference Compounds

4.3 Chemical Shift Scales

4.4 Magnetic Susceptibility Correction

4.5 Empirical Correlations of Chemical Shifts

4.6 Theory of Chemical Shifts

4.7 Effect of Electron Density

4.8 Magnetic Anisotropy and Chemical Shifts

4.9 Ring Currents

4.10 Nuclei Other Than Hydrogen

4.11 Carbon-13

4.12 Tabulations of Chemical Shifts and Spectra

4.13 Empirical Estimation of Chemical Shifts

4.14 Isotope Effects on Chemical Shifts

4.15 Paramagnetic Species

4.16 Lanthanide Shift Reagents

Problems

5. Electron-Coupled Spin-Spin Interactions

5.1 Origin of Spin-Spin Coupling

5.2 Coupling between Groups of Equivalent Nuclei

5.3 First-Order Analysis

5.4 Signs of Coupling Constants

5.5 Theory of Spin-Spin Coupling

5.6 Some Observed Coupling Constants

5.7 Correlation of Coupling Constants with Other Physical Properties

5.8 Tabulations of Coupling Constants

Problems

6. The Use of NMR in Structure Elucidation

6.1 A Systematic Approach to the Interpretation of NMR Spectra

6.2 Some Features of Carbon-13 Spectra

6.3 Structure Elucidation of Polymers

Problems

7. Analysis of Complex Spectra

7.1 Notation

7.2 Energy Levels and Transitions in an AX System

7.3 Quantum Mechanical Formalism

7.4 Nuclear Spin Basis Functions

7.5 The Spin Hamiltonian

7.6 The Two-Spin System without Coupling

7.7 Factoring the Secular Equation

7.8 Two Coupled Spins

7.9 Selection Rules and Intensities

7.10 The AB Spectrum

7.11 Spectral Contributions from Equivalent Nuclei

7.12 Symmetry of Wave Functions

7.13 Summary of Rules for Calculating Spectra

7.14 The Three-Spin System: ABC

7.15 The A2B System

7.16 The A3B System; Subspectral Analysis

7.17 The ABX System

7.18 Analysis of an ABX Spectrum

7.19 Relative Signs of JAX and JBX in an ABX Spectrum

7.20 ABX Patterns; Deceptively Simple Spectra

7.21 "Virtual Coupling"

7.22 The AB'BB' and AA'XX' Systems

7.23 Other Complex Spectra

7.24 Aids in the Analysis of Complex Spectra

7.25 Carbon-13 Satellites

7.26 Effects of Molecular Asymmetry

7.27 Polymer Configuration

7.28 Use of Liquid Crystals as Solvents

Problems

8. Relaxation

8.1 Molecular Motions and Processes for Relaxation in Liquids

8.2 Nuclear Magnetic Dipole Interactions

8.3 Relaxation via Chemical Shift Anisotropy

8.4 Spin-Rotation Relaxation

8.5 Electric Quadrupole Relaxation

8.6 Scalar Relaxation

8.7 Relaxation by Paramagnetic Substances

8.8 Some Chemical Applications

8.9 Measurement of Relaxation Times

Problems

9. Theory and Application of Double Resonance

9.1 Notation and Terminology

9.2 Experimental Techniques

9.3 Theory of Double Resonance

9.4 The Nuclear Overhauser Effect

9.5 Structure Elucidation

9.6 Location of "Hidden" Lines

9.7 Determination of Chemical Shifts

9.8 Relative Signs of Coupling Constants

9.9 Determination of Energy Level Arrangements

9.10 "High Resolution" Spectra in Solids

Problems

10. Pulse Fourier Transform Methods

10.1 RF Pulses and the Free Induction Decay

10.2 Fourier Transformation of the FID

10.3 Instrumental Requirements

10.4 Data Processing in the Computer

10.5 Sensitivity Enhancement by Time Averaging

10.6 Measurement of Relaxation Times

10.7 Two-Dimensional FT-NMR

Problems

11. Exchange Processes: Dynamic NMR

11.1 Spectra of Exchanging Systems

11.2 Theory of Chemical Exchange

11.3 Collapse of Spin Multiplets

11.4 More Complete Theories of Exchange

11.5 Double Resonance and Pulse Techniques

11.6 CIDNP

Problems

12. Solvent Effects and Hydrogen Bonding

12.1 Medium Effects on Chemical Shifts

12.2 Solvent Effects on Coupling Constants

12.3 Solvent Effects on Relaxation and Exchange Rates

12.4 Hydrogen Bonding

Problems

13. Use of NMR in Quantitative Analysis

13.1 Advantages of NMR in Quantitative Analysis

13.2 Drawbacks and Problems in the Use of NMR in Quantitative Analysis

13.3 Some Analytical Uses of NMR

14. Contemporary Developments in NMR

14.1 Solids

14.2 Multinuclear NMR

14.3 Biochemical Studies

14.4 NMR Imaging

References

Appendix A General NMR References

Appendix B Nuclear Spins, Magnetic Moments, and Resonance Frequencies

Appendix C Proton and Carbon-13 NMR Spectra of "Unknowns"

Appendix D Answers to Selected Problems

Index