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Solid-State NMR

Book Description

The power of nuclear magnetic resonance, NMR, for characterizing molecules dissolved in solution is widely acknowledged and NMR forms an essential component of undergraduate chemistry degrees. However, the application of NMR to the solid state is much less well appreciated. This text sets out the fundamental principles of solid-state NMR, explaining how NMR in solids differs from that in solution, showing how the various interactions of NMR can be manipulated to yield high-resolution spectra and to give information on local structure and dynamics in solids. This book aims to take some of the mystique out of solid-state NMR by providing a comprehensible discussion of the methodology, including the basic concepts and a practical guide to implementation of the experiments. A basic knowledge of solution-state NMR is assumed and is only briefly covered. The text is intended for those in academia and industry expecting to use solid-state NMR in their research and looking for an accessible introduction to the field. It will also be valuable for non-experts interested in learning how NMR can be usefully applied to solid systems. Detailed mathematical treatments are delayed to a chapter at the mid-point of the text and can be skipped. Introductions to experiments and numerical simulations are provided to help link NMR results to experimental practice. The different aspects of solid-state NMR, from basic pulse-and-acquire experiments to sophisticated techniques for the measurement of anisotropy information are presented. Examples illustrate the wide variety of applications of the technique and its complementarity to other solid-state characterization techniques such as X-ray diffraction. Various aspects of NMR crystallography are covered as are topics of motion in solids.

Table of Contents

  1. Cover
  2. Halftitle
  3. Title
  4. Copyright
  5. Contents
  6. PREFACE
  7. ABOUT THE AUTHORS
  8. 1 INTRODUCTION
    1. 1.1 The utility of NMR
    2. 1.2 A preview of solid-state NMR spectra
    3. 1.3 The solid state
      1. 1.3.1 Introduction
      2. 1.3.2 Symmetry in the crystalline state
      3. 1.3.3 Effects of crystal structure on NMR
      4. 1.3.4 Types of solids
    4. 1.4 Polymorphism, solvates, co-crystals & host:guest systems
    5. 1.5 NMR of solids & the periodic table
  9. 2 BASIC NMR CONCEPTS FOR SOLIDS
    1. 2.1 Nuclear spin magnetization
    2. 2.2 Tensors
    3. 2.3 Shielding
    4. 2.4 Indirect coupling
    5. 2.5 Dipolar coupling
    6. 2.6 Quadrupolar coupling
    7. 2.7 Magic-angle spinning
    8. 2.8 Relaxation
  10. 3 SPIN-1/2 NUCLEI: A PRACTICAL GUIDE
    1. 3.1 Introduction
    2. 3.2 The vector model & the rotating frame of reference
      1. 3.2.1 Pulse angle
    3. 3.3 The components of an NMR experiment
      1. 3.3.1 Recycle delay
      2. 3.3.2 Acquisition time
      3. 3.3.3 Receiver gain
      4. 3.3.4 Spectral width
      5. 3.3.5 Dead-time
      6. 3.3.6 Spinning sideband suppression
      7. 3.3.7 Decoupling
      8. 3.3.8 Spectral referencing
      9. 3.3.9 Temperature calibration
    4. 3.4 Cross polarization
      1. 3.4.1 The cross-polarization experiment
      2. 3.4.2 Contact time
      3. 3.4.3 Direct excitation or cross polarization? A summary
    5. 3.5 High-resolution spectra from 1H (& 19F)
  11. 4 QUANTUM MECHANICS OF SOLID-STATE NMR
    1. 4.1 Introduction
    2. 4.2 The Hamiltonians of NMR
      1. 4.2.1 Spin operators
      2. 4.2.2 Secular & non-secular terms
      3. 4.2.3 Coupling Hamiltonians
      4. 4.2.4 Radiofrequency & the rotating frame
    3. 4.3 The density matrix
    4. 4.4 Density operator treatments of simple NMR experiments
      1. 4.4.1 The basic NMR experiment
      2. 4.4.2 Echoes & coherence pathway diagrams
    5. 4.5 The density matrix for coupled spins
      1. 4.5.1 Example 1: A dipolar-coupled homonuclear spin pair
      2. 4.5.2 Example 2: Cross-polarization
    6. 4.6 Euler angles & spherical tensors
      1. 4.6.1 Magic-angle spinning
    7. 4.7 Additional analytical tools
      1. 4.7.1 Average Hamiltonian theory
      2. 4.7.2 An overview of Floquet theory
      3. 4.7.3 Introduction to irreducible spherical tensor operators
  12. 5 GOING FURTHER WITH SPIN- 1/2 SOLID-STATE NMR
    1. 5.1 Introduction
      1. 5.1.1 Spin- 1/2 NMR at high magnetic fields
      2. 5.1.2 Advanced heteronuclear decoupling
      3. 5.1.3 Advanced cross polarization
    2. 5.2 Linewidths in solid-state NMR
    3. 5.3 Exploiting indirect (J) couplings in solids
    4. 5.4 Spectral correlation experiments
      1. 5.4.1 Basic principles of two-dimensional NMR
      2. 5.4.2 Transfer of magnetization via dipolar couplings
      3. 5.4.3 Heteronuclear correlation
      4. 5.4.4 Homonuclear correlation
    5. 5.5 Homonuclear decoupling
      1. 5.5.1 Overview of homonuclear decoupling sequences
    6. 5.6 Using correlation experiments for spectral assignment
    7. 5.7 Further applications
      1. 5.7.1 Labeled systems
      2. 5.7.2 Quantitative applications
  13. 6 QUADRUPOLAR NUCLEI
    1. 6.1 Introduction
    2. 6.2 Characteristics of fi rst-order quadrupolar spectra
    3. 6.3 First-order energy levels & spectra
    4. 6.4 Second-order zero-asymmetry cases
      1. 6.4.1 Transition frequencies
      2. 6.4.2 Central-transition spectra: Static samples
      3. 6.4.3 Central-transition spectra: Rapid sample spinning
    5. 6.5 Spectra for cases with non-zero asymmetry: Central transition
    6. 6.6 Recording one-dimensional spectra of quadrupolar nuclei
      1. 6.6.1 Nutation
    7. 6.7 Manipulating the quadrupolar effect
      1. 6.7.1 Variable-angle spinning
      2. 6.7.2 Double rotation
      3. 6.7.3 Dynamic-angle spinning
      4. 6.7.4 Multiple quantum magic-angle spinning
      5. 6.7.5 Satellite transition magic-angle spinning
      6. 6.7.6 Summary for spectroscopy of half-integer quadrupolar nuclei
    8. 6.8 Spectra for integral spins
  14. 7 RELAXATION, EXCHANGE & QUANTITATION
    1. 7.1 Introduction
    2. 7.2 Relaxation
      1. 7.2.1 The cause of relaxation
      2. 7.2.2 Proton relaxation times
      3. 7.2.3 Lineshapes & linewidths for non-spinning samples
      4. 7.2.4 Relaxation & high-resolution measurements combined
      5. 7.2.5 Measuring relaxation times
    3. 7.3 Exchange
      1. 7.3.1 Positional exchange
      2. 7.3.2 Hydrogen exchange
      3. 7.3.3 Reorientation without a change in isotropic chemical shift
      4. 7.3.4 Diffusive motion
      5. 7.3.5 "Soft" solids
      6. 7.3.6 Interference
    4. 7.4 Quantitative NMR
      1. 7.4.1 Relative intensity
      2. 7.4.2 Absolute intensity
    5. 7.5 Paramagnetic systems
      1. 7.5.1 Relaxation effects
      2. 7.5.2 Shift effects
  15. 8 ANALYSIS & INTERPRETATION
    1. 8.1 Introduction
    2. 8.2 Quantitative measurement of anisotropies
      1. 8.2.1 General
      2. 8.2.2 Quantitation of powder lineshapes
      3. 8.2.3 Quantitation of spinning sideband manifolds
      4. 8.2.4 Single-crystal vs. polycrystalline samples
      5. 8.2.5 Resolving anisotropy information by isotropic shift
    3. 8.3 Measurement of dipolar couplings
      1. 8.3.1 Measurement of heteronuclear couplings
      2. 8.3.2 Measurement of homonuclear couplings
    4. 8.4 Quantifying indirect (J) couplings
    5. 8.5 Tensor interplay
    6. 8.6 Effects of quadrupolar nuclei on spin-1/2 spectra
    7. 8.7 Quantifying relationships between tensors
      1. 8.7.1 From one-dimensional spectra
      2. 8.7.2 From correlation spectra
      3. 8.7.3 Specialized experiments
    8. 8.8 NMR crystallography
      1. 8.8.1 Chemical examples
      2. 8.8.2 Computation of NMR parameters
  16. A THE SPIN PROPERTIES OF SPIN- 1/2 NUCLIDES
  17. B THE SPIN PROPERTIES OF QUADRUPOLAR NUCLIDES
  18. C LIOUVILLE SPACE, RELAXATION & EXCHANGE
    1. C.1 Introduction to Liouville space
    2. C.2 Application to relaxation
    3. C.3 Application to chemical exchange
  19. D INTRODUCTION TO SOLID-STATE NMR SIMULATION
    1. D.1 Specifying the spin system
    2. D.2 Specifying the powder sampling
    3. D.3 Specifying the pulse sequence
    4. D.4 Effi ciency of calculation
  20. INDEX
  21. Last Page
  22. Backcover