Solid-State NMR IV Methods and Applications of Solid-State NMR

209 Pages·1994·7.69 MB·English

by  Andrew E. Bennett, Robert G. Griffin (auth.), Prof. Dr. Bernhard Blümich (eds.)

NMR
33
Basic Principles and Progress
Editors:
P. Diehl E. Fluck H. GUnther R. Kosfeld J. Seelig
Guest-Editor: B. Bltimich
Advisory Board: G. Bodenhausen S. Forsen
R. K. Harris C. L. Khetrapal T. E. Lippmaa
G. J. Martin H. Pfeifer A. Pines B. L. Shapiro
Solid-State NMR IV
Methods and Applications
of Solid-State NMR
Guest-Editor: B. Bltimich
With contributions by
A. E. Bennett, B. F. Chmelka, H. Eckert,
R. G. Griffin, S. Vega, J. W. Zwanziger
With 112 Figures and 1 Table
Springer-Verlag
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ISBN-13:978-3-642-79129-1 e-ISBN-13:978-3-642-79127-7
DOl: 10.1007/978-3-642-79127-7
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© Springer-Verlag Berlin Heidelberg 1994
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Preface
Solid-State NMR is a branch of Nuclear Magnetic Resonance which
is presently experiencing a phase of strongly increasing popularity.
The most striking evidence is the large number of contributions from
Solid-State Resonance at NMR meetings, approaching that ofliquid
state resonance. Important progress can be observed in the areas of
methodological developments and applications to organic and
inorganic matter. One volume devoted to more or less one of each of
these areas has been published in the preceding three issues. This
volume can be considered an addendum to this series.
Selected methods and applications of Solid-State NMR are featured
in three chapters. The first one treats the recoupling of dipolar
interactions in solids, which are averaged by fast sample rotation.
Following an introduction to effective Hamiltonians and Floquet
theory, different types of experiment such as rotary resonance,
dipolar chemical shift correlation spectroscopy, rotational resonance
and multipulse recoupling are treated in the powerful Floquet
formalism. In the second chapter, the different approaches to line
narrowing of quadrupolar nuclei are reviewed in a. consistent
formulation of double resonance (DaR) and dynamic angle spinning
(DAS). Practical aspects of probe design are considered as well as
advanced 2D experiments, sensitivity enhancement techniques, and
spinning sideband manipulations. The use of such techniques
dramatically increases the number of nuclei which can be probed in
high resolution NMR spectroscopy. The final chapter describes new
experimental approaches and results of structural studies of
noncrystalline solids. A wide variety of solid-state techniques for
investigations of glasses is reviewed. Examples are wideline NMR,
MAS NMR, and 2D NMR including multiple quantum methods.
Application of these techniques to systematic studies of different
glasses are presented in the main part, illustrating the new frontiers in
understanding the complexity of glasses which can be explored by the
use of modern solid-state NMR methods.
The authors of this volume are thanked in particular for their
dedication in writing the contributions. Springer-Verlag has been
very helpful in its assistance and editorial supervision.
Aachen, May 1994 B.Bliimich
R. Kosfeld
Guest-Editor
Prof. Dr. Bernhard Bliimich
Lehrstuhl fUr Makromolekulare Chemie,
RTWH Aachen, Worringer Weg 1,
D-52056 Aachen, FRG
Editorial Board:
Prof. Dr. Peter Diehl Institut fUr Physik der Universitiit Basel, KlingelbergstraBe 82,
CH·4056 Basel
Prof. Dr. Ekkehard Fluck Gmelin-Institut, VarrentrappstraBe 40/42,
0-60486 Frankfurt am Main, FRG
Prof. Dr. H. GUnther Universitiit Siegen, Organische Chemie II,
Postfach 101240, 0-57076 Siegen, FRG
Prof. Dr. Robert Kosfeld In den Atzenbenden 30, 0-52080 Aachen, FRG
Prof. Dr. J. Seelig Biozentrum der Universitiit Basel, Abt. Biophysikalische
Chemie, KlingelbergstraBe 70, CH-4056 Basel
Advisory Board:
Prof. Dr. Section de chimie, Universire de Lausanne,
Geoffrey Bodenhausen Rue de la Barre 2, CH-1005 Lausanne
Prof. Dr. Sturse Forsen DepartrnentofPhysical Chemistry, Chemical Centre,
University of Lund, P.O.B. 740, S-22007 Lund
Prof. Dr. Robin K. Harris University of Durham, Department of Chemistry,
Science Laboratories, South Road, GB-Durham DHI 3LE
Prof. Dr. C. L Khetrapal Sophisticated Instruments Facility, Indian Institute of Science,
Bangalore-560012,India
Prof. Dr. T. E. Lippmaa Institute of Chemical Physics and Biophysics,
Academy of Sciences of the Estonian SSR, Lenini paiestee 10,
Tallinn 200001, Estonia
Prof. Dr. G. J. Martin Universire de Nantes, U.E.R. de Chimie,
Resonance Magnetique Nuclerure et Reactivire Chimique,
UA-CNRS No 472, 2, rue de la Houssiniere,
F-44072NantesCedex
Prof. Dr. Harry Pfeifer FachbereichPhysik, UniversitiitLeipzig,LinnestraBe5,
0-04103 Leipzig, FRG
Prof. Dr. Alex Pines University of California, Berkeley, Department of Chemistry,
Berkeley, CA 94720, USA
Prof. Dr. Bernard L Shapiro 966 Elsinore Court, Palo Alto, CA 94303, USA
Table of Contents
Recoupling of Homo- and Heteronuclear
Dipolar Interactions in Rotating Solids
A. E. Bennett, R. G. Griffin, S. Vega ............... .
Solid-State NMR Line Narrowing Methods
for Quadrupolar Nuclei: Double Rotation
and Dynamic-Angle Spinning
B. F. Chmelka, J. W. Zwanziger . . . . . . . . . . . . . . . . . . . .. 79
Structural Studies of Noncrystalline Solids
Using Solid State NMR. New Experimental
Approaches and Results
H. Eckert. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 125
Author Index Volumes 21 -33 ..................... 199
Tables of Contents to Volumes 30 and 31
Solid-State NMR I - Methods
Introduction to Solid-State NMR
A.-R. Grimmer, B. Bliimich
High-Resolution 13C NMR Investigations of Local
Dynamics in Bulk Polymers at Temperatures Below
and Above the Glass-Transition Temperature
F. Laupretre
Xenon NMR Spectroscopy
D. Raftery, B.F. Chmelka
NMR as a Generalized Incoherent Scattering Experiment
G. Fleischer, F. Fujara
NMR Imaging of Solids
P. Bliimler, B. Bliimich
Solid-State NMR II - Inorganic Matter
29Si NMR of Inorganic Solids
G. Engelhardt and H. Koller
NMR of Solid Surfaces
H. Pfeifer
MAS and CP/MAS NMR of Less Common
A. Sebald
Satellite Transition Spectroscopy of Quadrupolar
Nuclei
C. Jager
NMR-NQR Studies of High-Temperature
Superconductors
D. Brinkmann and M. Mali
Table of Contents to Volume 32
Solid State NMR III - Organic Matter
2H NMR Spectroscopy of Solids and Liquid Crystals
G. L. Hoatson, R. L. Void
Cross-Polarization, Relaxation Times
and Spin-Diffusion in Rotating Solids
D. Michel, F. Engelke
Solid-State NMR Techniques for the Study
of Polymer-Polymer Miscibility
W. S. Veeman, W. E. J. R. Maas
Two-Dimensional Exchange NMR Spectroscopy
in Polymer Research
H. W. Beckham, H. W. Spiess
Recoupling of Homo- and Heteronuclear
Dipolar Interactions in Rotating Solids
Andrew E. Bennett1, Robert G. Grillinl, and Shimon Vega2
1 Francis Bitter National Magnet Laboratory and Department of Chemistry,
Massachusetts Institute of Technology, Cambridge, MA 02139, USA
2Department of Chemical Physics, Weizmann Institute of Science, Rehovot 76100, Israel
Table of Contents
1 Introduction . 3
2 Theoretical Framework for Recoupling Experiments 5
2.1 The MAS Hamiltonian for Coupled Spin Systems 5
2.2 Fictitious Spin-Half Operators 9
2.3 Spin Evolution .... 10
2.4 Effective Spin Hamiltonians 12
2.4.1 The Toggling Frame 13
2.4.2 Average Hamiltonian Theory 14
2.4.3 Floquet Theory . . . . . 15
3 The Heteronuclear Dipolar Interaction 21
3.1 Isolated Heteronuclear Spin Pair under MAS 22
3.1.1 The Dipolar MAS Spectrum 22
3.1.2 The Dipolar Floquet Hamiltonian 26
3.2 Rotary Resonance Recoupling 28
3.3 Dipolar Chemical Shift Correlation Spectroscopy 34
3.4 Rotational Echo Double Resonance 39
3.4.1 Dipolar Dephasing Experiments 39
3.4.2 Transferred Echo Double Resonance 45
4 The Homonuclear Dipolar Interaction . . 46
4.1 Rotor Driven Recoupling .... 47
4.1.1 The Dipolar Floquet Hamiltonian 48
4.1.2 Lineshapes at Rotational Resonance 51
4.1.3 Magnetization Exchange Experiments 55
4.2 Multiple Pulse Recoupling 59
4.2.1 Solid Echo Recoupling 59
4.2.2 Spin Echo Techniques 63
5 Applications 69
6 Conclusions 73
7 References 74
NMR Basic Principles and Progress, Vol. 33
© Springer-Verlag, Berlin Heidelberg 1994
2 A. E. Bennett
In recent years, several new techniques have been developed to measure dipolar couplings in
powdered solids using magic angle spinning (MAS) NMR spectroscopy. These experiments have
made it possible to measure interatomic distances in polycrystalline and amorphous solids, providing
information about their molecular structure that is often difficult or impossible to obtain by other
methods. All of these approaches take advantage of the improved resolution and sensitivity of
«dilute" spins under MAS, and where appropriate, cross polarization and proton decoupling. In
addition, they involve the application of some means of restoring selected dipolar couplings to the
MAS experiment so that internuclear distances may be measured. In this article, a variety of
homo-and heteronuclear recoupling experiments are reviewed and analyzed within the frameworks
of Average Hamiltonian Theory (AHT) and Floquet Theory. Selected applications illustrating the
utility of these techniques are also discussed.