Introduction to Solid-State Nmr Spectroscopy

by Duer, Melinda J.

• ISBN13: 9781405109147
• ISBN10: 1405109149
• Edition: 1st
• Format: Paperback
• Copyright: 2005-07-29
• Publisher: Wiley-Blackwell

Summary

Introduction to Solid State NMR Spectroscopy is written for undergraduate and graduate students of chemistry, studying courses in nuclear magnetic resonance or undertaking research projects in this area. It will also serve as a useful introduction in industry, where researchers are turning to solid-state techniques to solve problems that are not amenable to other investigative techniques. By covering solid-state NMR spectroscopy in a clear, straightforward and approachable way with detailed descriptions of the major solid-state NMR experiments focussing on what the experiments do and what they tell the researcher, this book will serve as an ideal introduction to the subject. These descriptions are backed up by separate mathematical explanations for those who wish to gain a more sophisticated quantitative understanding of the phenomena. With additional coverage of the practical implementation of solid-state NMR experiments integrated into the discussion, this book will be essential reading for all those using, or about to use, solid-state NMR spectroscopy.

Author Biography

Dr Melinda Duer is a senior lecturer in the Department of Chemistry at the University of Cambridge, Cambridge, UK

Table of Contents

Preface	xii
Acknowledgements	xv
The Basics of NMR	1	(59)
The vector model of pulsed NMR	1	(4)
Nuclei in a static, uniform magnetic field	2	(1)
The effect of rf pulses	3	(2)
The quantum mechanical picture: hamiltonians and the Schrodinger equation	5	(24)
Quantum mechanics and NMR	6	(1)
Wavefunctions	6	(1)
Operators, physical observables and expectation values	7	(1)
Schrodinger's equation, eigenfunctions and eigenvalues	7	(1)
Spin operators and spin states	8	(3)
Dirac's bra-ket notation	11	(1)
Matrices	11	(1)
Nuclei in a static, uniform field	12	(3)
The effect of rf pulses	15	(4)
Exponential operators, rotation operators and rotations	19	(1)
Rotation of vectors, wavefunctions and operators (active rotations)	20	(3)
Rotation of axis frames	23	(2)
Representation of rf fields	25	(1)
Euler angles	25	(1)
Rotations with Euler angles	26	(1)
Rotation of Cartesian axis frames	27	(2)
The density matrix representation and coherences	29	(8)
Coherences and populations	30	(3)
The density operator at thermal equilibrium	33	(1)
Time evolution of the density matrix	34	(3)
Nuclear spin interactions	37	(6)
Interaction tensors	41	(2)
General features of Fourier transform NMR experiments	43	(17)
Multidimensional NMR	43	(3)
Phase cycling	46	(2)
Quadrature detection	48	(5)
The NMR spectrometer	53	(1)
Generating rf pulses	53	(3)
Detecting the NMR signal	56	(2)
Notes	58	(1)
References	59	(1)
Essential Techniques for Solid-State NMR	60	(56)
Introduction	60	(1)
Magic-angle spinning (MAS)	61	(16)
Spinning sidebands	62	(5)
Rotor or rotational echoes	67	(1)
Removing spinning sidebands	67	(5)
Setting the magic-angle and spinning rate	72	(3)
Magic-angle spinning for homonuclear dipolar couplings	75	(2)
Heteronuclear decoupling	77	(6)
High-power decoupling	78	(3)
Other heteronuclear decoupling sequences	81	(2)
Homonuclear decoupling	83	(13)
Implementing homonuclear decoupling sequences	83	(3)
Average hamiltonian theory and the toggling frame	86	(1)
Average hamiltonian theory	86	(3)
The toggling frame and the WAHUHA pulse sequence	89	(7)
Cross-polarization	96	(14)
Theory	97	(4)
Setting up the cross-polarization experiment	101	(5)
Cross-polarization and magic-angle spinning	106	(4)
Echo pulse sequences	110	(6)
Notes	113	(1)
References	114	(2)
Shielding and Chemical Shift: Theory and Uses	116	(35)
Theory	116	(9)
Introduction	116	(1)
The chemical shielding hamiltonian	117	(3)
Experimental manifestations of the shielding tensor	120	(3)
Definition of the chemical shift	123	(2)
The relationship between the shielding tensor and electronic structure	125	(6)
Measuring chemical shift anisotropies	131	(14)
Magic-angle spinning with recoupling pulse sequences	132	(3)
Variable-angle spinning experiments	135	(3)
Magic-angle turning	138	(3)
Two-dimensional separation of spinning sideband patterns	141	(4)
Measuring the orientation of chemical shielding tensors in the molecular frame for structure determination	145	(6)
Notes	149	(1)
References	149	(2)
Dipolar Coupling: Theory and Uses	151	(84)
Theory	151	(21)
Homonuclear dipolar coupling	154	(2)
Basis sets for multispin systems	156	(1)
The effect of homonuclear dipolar coupling on a spin system	157	(3)
Heteronuclear dipolar coupling	160	(2)
The effect of heteronuclear dipolar coupling on the spin system	162	(1)
Heteronuclear spin dipolar coupled to a homonuclear network of spins	163	(1)
The spherical tensor form of the dipolar hamiltonian	164	(1)
The dipolar hamiltonian in terms of spherical tensor operators	164	(1)
Spherical tensor operators	165	(2)
Interaction tensors	167	(1)
The homonuclear dipolar hamiltonian under static and MAS conditions	167	(5)
Introduction to the uses of dipolar coupling	172	(3)
Techniques for measuring homonuclear dipolar couplings	175	(32)
Recoupling pulse sequences	175	(5)
Analysis of the DRAMA pulse sequence	180	(4)
Simulating powder patterns from the DRAMA experiment	184	(1)
Double-quantum filtered experiments	185	(4)
Excitation of double-quantum coherence under magic-angle spinning	189	(2)
The form of the reconversion pulse sequence: the need for time-reversal symmetry	191	(4)
Analysis of the double-quantum filtered data	195	(1)
Analysis of the C7 pulse sequence for exciting double-quantum coherence in dipolar-coupled spin pairs	196	(3)
Rotational resonance	199	(3)
Theory of rotational resonance	202	(1)
Effect of HΔ term on the density operator	203	(1)
The hamiltonian in the new rotated frame	204	(1)
The average hamiltonian	205	(2)
Techniques for measuring heteronuclear dipolar couplings	207	(8)
Spin-echo double resonance (SEDOR)	207	(1)
Rotational-echo double resonance (REDOR)	208	(2)
Analysis of the REDOR experiment	210	(5)
Techniques for dipolar-coupled quadrupolar-spin-1/2 pairs	215	(5)
Transfer of population in double resonance (TRAPDOR)	216	(3)
Rotational-echo adiabatic-passage double-resonance (REAPDOR)	219	(1)
Techniques for measuring dipolar couplings between quadrupolar nuclei	220	(1)
Correlation experiments	221	(6)
Homonuclear correlation experiments for spin-1/2 systems	221	(3)
Homonuclear correlation experiments for quadrupolar spin systems	224	(2)
Heteronuclear correlation experiments for spin-1/2	226	(1)
Spin-counting experiments	227	(8)
The formation of multiple-quantum coherences	228	(3)
Implementation of spin-counting experiments	231	(1)
Notes	232	(1)
References	233	(2)
Quadrupole Coupling: Theory and Uses	235	(58)
Introduction	235	(2)
Theory	237	(18)
The quadrupole hamiltonian	237	(5)
The quadrupole hamiltonian in terms of spherical tensor operators: the effect of the rotating frame and magic-angle spinning	242	(1)
The quadrupole hamiltonian in terms of spherical tensor operators	242	(1)
The effect of the rotating frame: first- and second-order average hamiltonians for the quadrupole interaction	243	(5)
The energy levels under quadrupole coupling	248	(1)
The effect of magic-angle spinning	248	(1)
The effect of rf pulses	249	(3)
The effects of quadrupolar nuclei on the spectra of spin-1/2 nuclei	252	(3)
High-resolution NMR experiments for half-integer quadrupolar nuclei	255	(25)
Magic-angle spinning (MAS)	256	(3)
Double rotation (DOR)	259	(1)
Dynamic-angle spinning (DAS)	260	(3)
Multiple-quantum magic-angle spinning (MQMAS)	263	(5)
Satellite transition magic-angle spinning (STMAS)	268	(7)
Recording two-dimensional datasets for DAS, MQMAS and STMAS	275	(5)
Other techniques for half-integer quadrupole nuclei	280	(13)
Quadrupole nutation	282	(3)
Cross-polarization	285	(5)
Notes	290	(1)
References	291	(2)
NMR Techniques for Studying Molecular Motion in Solids	293	(43)
Introduction	293	(3)
Powder lineshape analysis	296	(17)
Simulating powder pattern lineshapes	297	(8)
Resolving powder patterns	305	(6)
Using homonuclear dipolar-coupling lineshapes - the WISE experiment	311	(2)
Relaxation time studies	313	(3)
Exchange experiments	316	(6)
Achieving pure absorption lineshapes in exchange spectra	318	(2)
Interpreting two-dimensional exchange spectra	320	(2)
2H NMR	322	(14)
Measuring 2H NMR spectra	323	(5)
2H lineshape simulations	328	(1)
Relaxation time studies	329	(1)
2H exchange experiments	330	(2)
Resolving 2H powder patterns	332	(2)
Notes	334	(1)
References	335	(1)
Appendix A NMR Properties of Commonly Observed Nuclei	336	(1)
Appendix B The General Form of a Spin Interaction Hamiltonian in Terms of Spherical Tensors and Spherical Tensor Operators	337	(6)
References	343	(1)
Index	344