CONTENTS

Page No.

Acknowledgements

Abstract

Abbreviations

Chapter 1 : Introduction to Solid State NMR and Methods for the Determination of

Chemical Shielding and Electric Field Gradient Tensors

1.1 Introduction 2

1.2 Spin Interactions in Solid State NMR 3

1.2.1 Spherical Tensor Formalism 5

1.2.2 Euler Angles and Coordinate Transformation 5

1.2.3 Chemical Shielding Interaction 8

1.2.4 Magic Angle Sample Spinning 11

1.2.5 Dipolar Interaction 15

1.2.6 J-coupling Interaction 16

1.2.7 Quadrupolar Interaction 18

1.2.7.1 Quadrupole Hamiltonian 20

1.2.7.2 Spin 1 21

1.2.7.3 Half-integer (n/2) Quadrupolar Nuclei 23

1.3 Experimental Techniques Used 28

1.3.1 Cross-Polarization Magic Angle Spinning (CP-MAS) 28

1.3.2 Two Dimensional Magic Angle Turning 30

1.3.3 3Q-MAS: Three-pulse z-filter Sequence 31

1.3.3.1 Determination of CS and EFG Parameters 33

1.4 Quantum Chemical Calculations of NMR Interaction Tensors 35

1.4.1 Overview of ab initio Theory 36

1.4.1.1 The Hartree-Fock Method 37

1.4.1.2 Density Functional Theory 39

1.4.1.3 Self-consistent Field Method 40

1.4.2 Basis Sets 42

1.4.2.1 Gaussian-type Orbitals 42

1.4.2.2 Plane Waves and Methods 44

Pseudopotential Method 45

Augmented Plane Wave Method 45

Linear Augmented Plane Wave Method 48

1.4.3 Determination of Chemical Shielding Tensors 49

1.4.4 Determination of Electric Field Gradient Tensors 53

1.4.5 Computational Resources 55

1.4.6 Computational Details 57

1.5 References 60

Chapter 2: Experimental Determination and ab initio Calculation of 31P

Chemical Shielding and 23Na EFG Tensors in Disodium 5'-Adenosine Triphosphate
Trihydrate

2.1 Introduction : 69

2.2 Solid State NMR Spectroscopy 71

Crystallization of ATP(5’)Na2.3H2O: 72

2.3 Structural Aspects 73

2.4 Experimental Determination of 31P Shielding

Tensors in ATP(5')Na.3H2O 75
 31
2.4.1 P Signal Assignments 76
31
2.4.2 P Shielding Tensors from 2D MAT 78

2.5 ab initio Calculation of 31P Shielding Tensors 81

2.5.1 Cluster Model for ATP(5')Na.3H2O 81

31
2.5.2 P Chemical Shielding Calculations 82

2.6 Experimental Determination of 23Na EFGs in ATP(5’)Na2.3H2O 89

23
2.7 Na EFG Tensors from ab initio Calculations 92
2.8 Conclusions 95
2.9 References 96

Chapter 4: LAPW Calculations of 14N, 17O and 27Al Electric Field Gradients in

Biomolecules and Aluminum Phosphates

4.1 Introduction

4.2 Periodic EFG Calculations using Linear Augmented Wave Approach

14
4.3 N Electric Field Gradients in Biomolecules and Related Compounds

4.3.1 Determination of Tensor Orientation in Glycyl-Glycine

17
4.4 O Electric Field Gradients in Biomolecules
27
4.5 Al EFG Calculation in AlPO4-14 and 3Q-MAS Assignment

4.6 Conclusions

References

Chapter 3: Experimental Determination and ab initio Calculation of Chemical

Shielding Tensors in Molecular Sieves ZSM-5 and ETS-10

3.1 Introduction
3.2 Solid State NMR
 29
3.3 Si Chemical Shielding and Local Structural Characteristics of ZSM-5

3.3.1 Structural Aspects

3.3.2 Experimental Determination of 29Si Chemical Shielding in ZSM-5
3.3.2.1 29Si Isotropic Chemical Shifts Determined from 29Si MAS
3.3.3 Theoretical Determination of 29Si Shielding Tensors un ZSM-5
3.3.3.1 Cluster Models
3.3.3.2 ab initio Calculations
29
3.4 Si Chemical Shielding and Local Structural Characteristics of ETS-10
3.4.1 Structure of ETS-10
3.4.2 Experimental Determination of 29Si Shielding Tensors in ETS-10
3.4.3 Theoretical Determination of 29Si Shielding Tensors in ETS-10

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14 17 27
Chapter 4: LAPW Calculations of N, O and Al Electric Field Gradients in
Biomolecules and Aluminum Phosphates

4.3 Introduction

4.4 Periodic EFG Calculations using Linear Augmented Wave Approach

14
3.3 N Electric Field Gradients in Biomolecules and Related Compounds

3.3.1 Determination of Tensor Orientation in Glycyl-Glycine

17
3.4 O Electric Field Gradients in Biomolecules

3.5 27Al EFG Calculation in AlPO4-14 and 3Q-MAS Assignment

3.6 Conclusions

3.7 References