NMR of Quadrupolar Nuclei in Solid Materials E-Book

Roderick E. Wasylishen

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Serie: EMR Books
• Sprache: Englisch

Seitenzahl: 1388

Veröffentlichungsjahr: 2012

Beschreibung

NMR OF QUADRUPOLAR NUCLEI IN SOLID MATERIALS

Over the past 20 years technical developments in superconducting magnet technology and instrumentation have increased the potential of NMR spectroscopy so that it is now possible to study a wide range of solid materials. In addition, one can probe the nuclear environments of many other additional atoms that possess the property of spin. In particular, it is possible to carry out NMR experiments on isotopes that have nuclear spin greater that ½ (i.e. quadrupolar nuclei). Since more that two-thirds of all NMR active isotopes are quadrupolar nuclei, applications of NMR spectroscopy with quadrupolar nuclei are increasing rapidly.

The purpose of this handbook is to provide under a single cover the fundamental principles, techniques and applications of quadrupolar NMR as it pertains to solid materials. Each chapter has been prepared by an expert who has made significant contributions to out understanding and appreciation of the importance of NMR studies of quadrupolar nuclei in solids. The text is divided into three sections: The first provides the reader with the background necessary to appreciate the challenges in acquiring and interpreting NMR spectra of quadrupolar neclei in solids. The second presents cutting-edge techniques and methodology for employing these techniques to investigate quadrupolar nuclei in solids. The final section explores applications of solid-state NMR studies of solids ranging from investigations of dynamics, characterizations of biological samples, organic and inorganic materials, porous materials, glasses, catalysts, semiconductors and high-temperature superconductors.

About EMR Handbooks

The Encyclopedia of Magnetic Resonance (EMR) publishes a wide range of online articles on all aspects of magnetic resonance in physics, chemistry, biology and medicine. The existence-of this large number of articles, written by experts in various fields, is enabling the publication of a series of EMR Handbooks on specific areas of NMR and MRI. The chapters of each of these handbooks will comprise a carefully chosen selection of Encyclopedia articles. In consultation with the EMR Editorial Board, the EMR Handbooks are coherently planned in advance by ­specially-selected Editors, and new articles, are written (together with updates of some already existing articles) to give appropriate complete coverage. The handbooks are intended to be of value and interest to research students, postdoctoral fellows and other researchers learning about the scientific area in question and undertaking relevant experiments, whether in ­academia or industry.

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Leseprobe

EMR Handbooks

Based on the Encyclopedia of Magnetic Resonance (EMR), this monograph series focuses on hot topics and major developments in modern magnetic resonance and its many applications. Each volume in the series will have a specific focus in either general NMR or MRI, with coverage of applications in the key scientific disciplines of physics, chemistry, biology or medicine. All the material published in this series, plus additional content, will be available in the online version of EMR, although in a slightly different format.

Previous EMR Handbooks

NMR CrystallographyEdited by Robin K. Harris, Roderick E. Wasylishen, Melinda J. DuerISBN 978-0-470-69961-4

Multidimensional NMR Methods for the Solution StateEdited by Gareth A. Morris, James W. EmsleyISBN 978-0-470-77075-7

Solid-State NMR Studies of BiopolymersEdited by Ann E. McDermott, Tatyana PolenovaISBN 978-0-470-72122-3

Forthcoming EMR Handbooks

RF Coils for MRIEdited by J. Thomas Vaughan and John R. GriffithsISBN 978-0-470-77076-4

UTE ImagingEdited by Graeme M. Bydder, Gary Fullerton and Ian R. YoungISBN 978-0-470-68835-9

Encyclopedia of Magnetic Resonance

Edited by Robin K. Harris, Roderick E. Wasylishen, Edwin D. Becker, John R. Griffiths, Vivian S. Lee, Ian R. Young, Ann

E. McDermott, Tatyana Polenova, James W. Emsley, George A. Gray, Gareth A. Morris, Melinda J. Duer and Bernard C. Gerstein.

The Encyclopedia of Magnetic Resonance (EMR) is based on the original printed Encyclopedia of Nuclear Magnetic Resonance, which was first published in 1996 with an update volume added in 2000. EMR was launched online in 2007 with all the material that had previously appeared in print. New updates have since been and will be added on a regular basis throughout the year to keep the content up to date with current developments. Nuclear was dropped from the title to reflect the increasing prominence of MRI and other medical applications. This allows the editors to expand beyond the traditional borders of NMR to MRI and MRS, as well as to EPR and other modalities. EMR covers all aspects of magnetic resonance, with articles on the fundamental principles, the techniques and their applications in all areas of physics, chemistry, biology and medicine for both general NMR and MRI. Additionally, articles on the history of the subject are included.

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Library of Congress Cataloging-in-Publication Data

NMR of quadrupolar nuclei in solid materials / editors, Roderick E. Wasylishen, Sharon E. Ashbrook, Stephen Wimperis.

    p. cm.

Includes Index.

ISBN 978-0-470-97398-l (cloth)

1. Nulclear quadrupole resonance spectroscopy. 2. Nuclear spin. 3. Solids–Analysis.

I. Wasylishen, Roderick E. II. Ashbrook, Sharon E. III. Wimperis, Stephen.

QD96.N84N57 2012 538’.362–dc23

2012002021

A catalogue record for this book is available from the British Library.

ISBN-13: 978-0-470-97398-1

Set in 9.5/11.5 pt Times by Laserwords (Private) Limited, Chennai, India Printed and bound in Singapore by Markono Print Media Pte Ltd

Encyclopedia of Magnetic Resonance

Editorial Board

Editors-in-Chief

Robin K. HarrisUniversity of DurhamDurhamUK

Roderick E. WasylishenUniversity of AlbertaEdmonton, AlbertaCanada

Section EditorsSOLID-STATE NMR & PHYSICS

Melinda J. DuerUniversity of CambridgeCambridgeUK

Bernard C. GersteinAmes, IAUSA

SOLUTION-STATE NMR & CHEMISTRY

James W. EmsleyUniversity of SouthamptonSouthamptonUK

George A. GrayVarian Inc.Palo Alto, CAUSA

Gareth A. MorrisUniversity of ManchesterManchesterUK

BIOCHEMICAL NMR

Ann E. McDermottColumbia UniversityNew York, NYUSA

Tatyana PolenovaUniversity of DelawareNewark, DEUSA

MRI & MRS

John R. GriffithsCancer Research UK   Cambridge Research   InstituteCambridgeUK

Vivian S. LeeNYU Langone Medical   CenterNew York, NYUSA

Ian R. YoungImperial CollegeLondonUK

HISTORICAL PERSPECTIVES

Edwin D. BeckerNational Institutes of HealthBethesda, MDUSA

International Advisory Board

David M. Grant (Chairman)University of UtahSalt Lake City, UTUSA

Isao AndoTokyo Institute   of TechnologyTokyoJapan

Adriaan BaxNational Institutes of HealthBethesda, MDUSA

Chris BoeschUniversity of BernBernSwitzerland

Paul A. BottomleyJohns Hopkins UniversityBaltimore, MDUSA

William G. BradleyUCSD Medical CenterSan Diego, CAUSA

Graeme M. BydderUCSD Medical CenterSan Diego, CAUSA

Paul T. CallaghanVictoria University   of WellingtonWellingtonNew Zealand

Richard R. ErnstEidgenössische Technische   Hochschule (ETH)ZürichSwitzerland

Ray FreemanUniversity of CambridgeCambridgeUK

Lucio FrydmanWeizmann Institute   of ScienceRehovotIsrael

Maurice GoldmanVillebon sur YvetteFrance

Harald GüntherUniversität SiegenSiegenGermany

Herbert Y. KresselHarvard Medical SchoolBoston, MAUSA

C. Leon PartainVanderbilt University Medical   CenterNashville, TNUSA

Alexander PinesUniversity of California   at BerkeleyBerkeley, CAUSA

George K. RaddaUniversity of OxfordOxfordUK

Hans Wolfgang SpiessMax-Planck Institute   of Polymer ResearchMainzGermany

Charles P. SlichterUniversity of Illinois   at Urbana-ChampaignUrbana, ILUSA

John S. WaughMassachusetts Institute   of Technology (MIT)Cambridge, MAUSA

Bernd WrackmeyerUniversität BayreuthBayreuthGermany

Kurt WüthrichThe Scripps Research   InstituteLa Jolla, CAUSAandETH ZürichZürichSwitzerland

Contents

Title

Copyright

Contributors

Series Preface

Volume Preface

Part A: Basic Principles

1 Quadrupolar InteractionsPascal P. Man

1.1 Introduction

1.2 Quadrupolar Hamiltonian in a Uniform Space

1.3 Spherical Tensor Representation for the Quadrupolar Hamiltonian

1.4 Quadrupolar Interaction as a Perturbation of Zeeman Interaction

1.5 Energy Levels and the Spectrum of a Single Crystal

1.6 Powder Spectrum

1.7 Appendix

2 Quadrupolar Nuclei in SolidsAlexander J. Vega

2.1 Introduction

2.2 Basic Spin Properties

2.3 Interaction with Radiofrequency Fields

2.4 Experimental Methods

2.5 Theory

3 Quadrupolar Coupling: An Introduction and Crystallographic AspectsSharon E. Ashbrook, Stephen Wimperis

3.1 Introduction

3.2 Theory of Quadrupolar Coupling

3.3 Computation of Quadrupolar Parameters

3.4 Effect on NMR Spectra

3.5 Measurement By NMR

3.6 Use in NMR Crystallography

3.7 Conclusions

4 Quadrupolar Nuclei in Solids: Influence of Different Interactions on SpectraDavid L. Bryce, Roderick E. Wasylishen

4.1 Introduction

4.2 Rules of Thumb for Interpreting the Solid-State NMR Spectra of Quadrupolar Nuclei

4.3 Influence of the Magnetic Shielding Interaction on Solid-State NMR Spectra of Quadrupolar Nuclei

4.4 Influence of Spin–Spin Coupling Interactions on Solid-State NMR Spectra of Quadrupolar Nuclei

4.5 Conclusions

Part B: Advanced Techniques

5 Acquisition of Wideline Solid-State NMR Spectra of Quadrupolar NucleiRobert W. Schurko

5.1 Introduction

5.2 Systems for Study by Ultra-Wideline NMR Spectroscopy

5.3 Methodologies for Acquisition of Ultra-Wideline NMR Spectra

5.4 Applications of UW SSNMR

5.5 Conclusions

6 Sensitivity and Resolution Enhancement of Half-Integer Quadrupolar Nuclei in Solid-State NMRThomas T. Nakashima, Roderick E. Wasylishen

6.1 Introduction

6.2 Single-Crystal Energy Levels, Populations, and Detection

6.3 Methods of Altering Populations

6.4 From Single Crystals to Powders

6.5 Sensitivity Enhancement for Powdered Samples

6.6 Application of Hyperbolic Secant Pulses in Resolution Enhancement

6.7 Concluding Remarks

7 Quadrupolar Nutation SpectroscopyArno P.M. Kentgens

7.1 Introduction

7.2 Spin Hamiltonians and Density Matrix

7.3 Practical Considerations

7.4 Applications of Nutation NMR Spectroscopy

7.5 Quantitative Spectra and Nutation-Based Filtering

8 Dynamic Angle SpinningPhilip J. Grandinetti

8.1 Introduction

8.2 Basic Principles

8.3 Implementation

8.4 Applications

9 Double Rotation (DOR) NMRRay Dupree

9.1 Introduction

9.2 Information from One Dimensional Dor Experiments

9.3 Two Dimensional Dor Experiments

9.4 Concluding Remarks

10 MQMAS NMR: Experimental StrategiesJean-Paul Amoureux, Marek Pruski

10.1 Introduction

10.2 Theoretical Background

10.3 Detection of Pure-Phase Spectra

10.4 Processing and Interpretation of Mqmas Spectra

10.5 Measurements of Heteronuclear Correlations

10.6 Sensitivity Enhancement via CPMG

10.7 Conclusion

11 STMAS NMR: Experimental AdvancesSharon E. Ashbrook, Stephen Wimperis

11.1 Introduction

11.2 Theoretical Background

11.3 Experimental Implementation

11.4 Double-Quantum Filtered Stmas (DQF-STMAS)

11.5 Stmas with Self-Compensation for Angle Misset (SCAM-STMAS)

11.6 Startmas and Other ‘Ultrafast’ Methods

11.7 Motional Broadening in STMAS

11.8 Higher-Order Interactions in STMAS

11.9 Applications of STMAS

11.10 Conclusions

12 Correlation Experiments Involving Half-Integer Quadrupolar NucleiMichael Deschamps, Dominique Massiot

12.1 Introduction

12.2 The Special Case of Quadrupolar Nuclei

12.3 J-Coupling and Residual Splitting

12.4 Experiments using J-Couplings

12.5 Dipolar Couplings

12.6 Conclusion

13 Computing Electric Field Gradient TensorsJosef W. Zwanziger

13.1 Introduction

13.2 Models of the Charge Distribution

13.3 Summary and Conclusions

Part C: Applications

14 Quadrupolar NMR to Investigate Dynamics in Solid MaterialsLuke A. O’Dell, Christopher I. Ratcliffe

14.1 Introduction

14.2 Deuterium

14.3 Nitrogen-14

14.4 Oxygen-17

14.5 Lithium

14.6 Multiple-Quantum Experiments

14.7 Concluding Remarks

15 Alkali Metal NMR of Biological MoleculesGang Wu

15.1 Introduction

15.2 Solid-State NMR for Alkali Metal Ions

15.3 Detection of Alkali Metal Ions in Biological Molecules

15.4 Concluding Remarks

16 Nitrogen-14 NMR Studies of Biological SystemsLuminita Duma

16.1 Introduction

16.2 Theoretical Background

16.4 Indirect Detection of 14N

16.5 Applications

16.6 Summary

17 Oxygen-17 NMR Studies of Organic and Biological MoleculesGang Wu

17.1 Introduction

17.2 Solid-State 17O NMR Techniques

17.3 Characterization of 17O NMR Tensors in Organic Functional Groups

17.4 Recent Advances in 17O NMR of Large Biological Molecules

17.5 Concluding Remarks

18 Oxygen-17 NMR of Inorganic MaterialsSharon E. Ashbrook, Mark E. Smith

18.1 General Introduction

18.2 Background and Technique Developments Enabling 17O NMR

18.3 Systems and Materials

18.4 Summary and Prospects

19 Chlorine, Bromine, and Iodine Solid-State NMRDavid L. Bryce, Cory M. Widdifield, Rebecca P. Chapman, Robert J. Attrell

19.1 Introduction and NMR Properties of the Quadrupolar Halogens

19.2 Experimental Aspects

19.3 Representative Quadrupolar and Chemical Shift Data and Discussion of Applications

19.4 Conclusions and Future Prospects

20 Quadrupolar NMR of Ionic Conductors, Batteries, and other Energy-Related MaterialsFrédéric Blanc, Leigh Spencer, Gillian R. Goward

20.1 Introduction

20.2 Structure Determination

20.3 Dynamics

20.4 Summary

21 Quadrupolar NMR of Nanoporous MaterialsMohamed Haouas, Charlotte Martineau, Francis Taulelle

21.1 Introduction

21.2 Most Useful Nuclei

21.3 NMR Characterization Strategies for Nanoporous Materials

21.4 Conclusions

22 Quadrupolar NMR in the Earth SciencesJonathan F. Stebbins

22.1 Introduction

22.2 Minerals as Model Compounds

22.3 Site Occupancies in Disordered Crystalline Solid Solutions

22.4 Silicate Glasses and Melts

22.5 Dynamics and Kinetics

22.6 Minerals Containing Unpaired Electron Spins

23 Quadrupolar NMR of SuperconductorsNicholas J. Curro

23.1 Introduction

23.2 Quadrupolar Spectra

23.3 Spin–Lattice Relaxation in a Superconductor

23.4 NQR in Superconductors

23.5 Antiferromagnetism and Superconductivity

23.6 Charged Vortices in High-Temperature Superconductors

23.7 Summary and Future Directions

24 Quadrupolar NMR of SemiconductorsJames P. Yesinowski

24.1 Introduction

24.2 Background

24.3 NMR Spin Hamiltonian in Semiconductors

24.4 Spin–Lattice Relaxation of Quadrupolar Nuclei

24.5 Quadrupolar Interactions—Effects and Applications

25 Quadrupolar NMR of Metal Nuclides in Biological MaterialsTatyana Polenova, Andrew S. Lipton, Paul D. Ellis

25.1 Introduction

25.2 Experimental Approaches for Quadrupolar Metal NMR in Biological Systems

25.3 Interpretation of NMR Parameters in Terms of Molecular Structure: Quantum Chemical Calculations

25.4 Examples of Applications in Biological Systems

25.5 Conclusions

26 Nuclear Waste Glasses: Insights from Solid-State NMRScott Kroeker

26.1 Introduction

26.2 Nuclides of Interest in Nuclear Waste Glasses

26.3 Characterization of Nuclear Waste Glasses

26.4 Future Outlook and Challenges

27 Quadrupolar Metal NMR of Oxide Materials Including CatalystsOlga B. Lapina, Victor V. Terskikh

27.1 Introduction

27.2 Metal Coordination Environment and NMR Parameters in Oxides

27.3 Ab Initio Calculations

27.4 Paramagnetic Effects

27.5 Examples of Quadrupolar Metal NMR in Materials Science

27.6 Applications in Glasses

27.7 Applications in Heterogeneous Catalysis

28 Quadrupolar NMR of Intermetallic CompoundsFrank Haarmann

28.1 Introduction

28.2 Background Concepts

28.3 Applications

Index

Contributors

Jean-Paul Amoureux

Université de Lille, Villeneuve d’Ascq 59650, France

Chapter 10: MQMAS NMR: Experimental Strategies

Sharon E. Ashbrook

School of Chemistry and EaStCHEM, University of St Andrews, St Andrews KY16 9ST, UK

Chapter 3: Quadrupolar Coupling: An Introduction and Crystallographic AspectsChapter 11: STMAS NMR: Experimental AdvancesChapter 18: Oxygen-17 NMR of Inorganic Materials

Robert J. Attrell

Department of Chemistry and Centre for Catalysis Research and Innovation, University of Ottawa, 10 Marie Curie Private, Ottawa, ON K1N 6N5, Canada

Chapter 19: Chlorine, Bromine, and Iodine Solid-State NMR

Frédéric Blanc

Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK

Chapter 20: Quadrupolar NMR of Ionic Conductors, Batteries, and other Energy-Related Materials

David L. Bryce

Department of Chemistry and Centre for Catalysis Research and Innovation, University of Ottawa, 10 Marie Curie Private, Ottawa, ON K1N 6N5, Canada

Chapter 4: Quadrupolar Nuclei in Solids: Influence of Different Interactions on SpectraChapter 19: Chlorine, Bromine, and Iodine Solid-State NMR

Rebecca P. Chapman

Department of Chemistry and Centre for Catalysis Research and Innovation, University of Ottawa, 10 Marie Curie Private, Ottawa, ON K1N 6N5, Canada

Chapter 19: Chlorine, Bromine, and Iodine Solid-State NMR

Nicholas J. Curro

Department of Physics, University of California, Davis, CA 95616, USA

Chapter 23: Quadrupolar NMR of Superconductors

Michael Deschamps

Département de Chimie, Université d’Orléans, BP 6759, 1 Rue de Chartres, 45067 Orléans cedex 2, France

Chapter 12: Correlation Experiments Involving Half-IntegerQuadrupolar Nuclei

Luminita Duma

Ecole Normale Supérieure, Départment de Chimie, Laboratoire des BioMolécules, UMR 7203 CNRS-ENS-UPMC, 24 rue Lhomond, 75005 Paris, FranceUniversité Pierre et Marie Curie Paris 6, 4 Place Jussieu, 75005 Paris, France

Chapter 16: Nitrogen-14 NMR Studies of Biological Systems

Ray Dupree

Department of Physics, University of Warwick, Coventry CV4 7AL, UK

Chapter 9: Double Rotation (DOR) NMR

Paul D. Ellis

Biological Sciences Division, K8-98, Pacific Northwest National Laboratory, Richland, WA 99352, USA

Chapter 25: Quadrupolar NMR of Metal Nuclides in Biological Materials

Gillian R. Goward

Department of Chemistry and Brockhouse Institute for Materials Research, McMaster University, Hamilton, ON L8S 4M1, Canada

Chapter 20: Quadrupolar NMR of Ionic Conductors, Batteries, and other Energy-Related Materials

Philip J. Grandinetti

Department of Chemistry, The Ohio State University, Columbus, OH 43210-1185, USA

Chapter 8: Dynamic Angle Spinning

Frank Haarmann

Institute of Inorganic Chemistry, RWTH Aachen University, Aachen D-52074, Germany

Chapter 28: Quadrupolar NMR of Intermetallic Compounds

Mohamed Haouas

Tectospin, Institut Lavoisier de Versailles, Université de Versailles-St. Quentin en Yvelines, 78035 Versailles, France

Chapter 21: Quadrupolar NMR of Nanoporous Materials

Arno P.M. Kentgens

Radboud University Nijmegen, Institute for Molecules and Materials, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands

Chapter 7: Quadrupolar Nutation Spectroscopy

Scott Kroeker

Department of Chemistry, University of Manitoba, Winnipeg, MB R3T 2N2, Canada

Chapter 26: Nuclear Waste Glasses: Insights from Solid-State NMR

Olga B. Lapina

Boreskov Institute of Catalysis, Russian Academy of Sciences, Prospect Lavrent’eva 5, Novosibirsk 630090, Russia

Chapter 27: Quadrupolar Metal NMR of Oxide Materials Including Catalysts

Andrew S. Lipton

Biological Sciences Division, K8-98, Pacific Northwest National Laboratory, Richland, WA 99352, USA

Chapter 25: Quadrupolar NMR of Metal Nuclides in Biological Materials

Pascal P. Man

Université Pierre et Marie Curie, Paris 94200, France

Chapter 1: Quadrupolar Interactions

Charlotte Martineau

Tectospin, Institut Lavoisier de Versailles, Université de Versailles-St. Quentin en Yvelines, 78035 Versailles, France

Chapter 21: Quadrupolar NMR of Nanoporous Materials

Dominique Massiot

CNRS-CEMHTI, Site Hautes Températures, 1D Avenue de la Recherche Scientifique, 45071 Orléans cedex 2, France

Chapter 12: Correlation Experiments Involving Half-IntegerQuadrupolar Nuclei

Thomas T. Nakashima

Department of Chemistry, University of Alberta, Edmonton, AB T6G 2G2, Canada

Chapter 6: Sensitivity and Resolution Enhancement of Half-IntegerQuadrupolar Nuclei in Solid-State NMR

Luke A. O’Dell

Steacie Institute for Molecular Sciences, National Research Council of Canada, 100 Sussex Drive, Ottawa, ON K1A 0R6, Canada

Chapter 14: Quadrupolar NMR to Investigate Dynamics in Solid Materials

Tatyana Polenova

Department of Chemistry and Biochemistry, 036 Brown Laboratories, University of Delaware, Newark, DE 19716, USA

Chapter 25: Quadrupolar NMR of Metal Nuclides in Biological Materials

Marek Pruski

Department of Chemistry, Ames Laboratory, Iowa State University, Ames, IA 50011, USA

Chapter 10: MQMAS NMR: Experimental Strategies

Christopher I. Ratcliffe

Steacie Institute for Molecular Sciences, National Research Council of Canada, 100 Sussex Drive, Ottawa, ON K1A 0R6, Canada

Chapter 14: Quadrupolar NMR to Investigate Dynamics in Solid Materials

Robert W. Schurko

University of Windsor, Department of Chemistry and Biochemistry, Windsor, ON N9B 3P4, Canada

Chapter 5: Acquisition of Wideline Solid-State NMR Spectra of Quadrupolar Nuclei

Mark E. Smith

Department of Physics, University of Warwick, Coventry CV4 7AL, UK

Chapter 18: Oxygen-17 NMR of Inorganic Materials

Leigh Spencer

Department of Chemistry and Brockhouse Institute for Materials Research, McMaster University, Hamilton, ON L8S 4M1, Canada

Chapter 20: Quadrupolar NMR of Ionic Conductors, Batteries, and other Energy-Related Materials

Jonathan F. Stebbins

Department of Geological and Environmental Sciences, Stanford University, Stanford, CA 94305, USA

Chapter 22: Quadrupolar NMR in the Earth Sciences

Francis Taulelle

Tectospin, Institut Lavoisier de Versailles, Université de Versailles-St. Quentin en Yvelines, 78035 Versailles, France

Chapter 21: Quadrupolar NMR of Nanoporous Materials

Victor V. Terskikh

Steacie Institute for Molecular Sciences, National Research Council Canada, Ottawa, ON K1A 0R6, Canada

Chapter 27: Quadrupolar Metal NMR of Oxide Materials Including Catalysts

Alexander J. Vega

Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716, USA

Chapter 2: Quadrupolar Nuclei in Solids

Roderick E. Wasylishen

Department of Chemistry, University of Alberta, Edmonton, AB T6G 2G2, Canada

Chapter 4: Quadrupolar Nuclei in Solids: Influence of Different Interactions on SpectraChapter 6: Sensitivity and Resolution Enhancement of Half-Integer Quadrupolar Nuclei in Solid-State NMR

Cory M. Widdifield

Department of Chemistry and Centre for Catalysis Research and Innovation, University of Ottawa, 10 Marie Curie Private, Ottawa, ON K1N 6N5, Canada

Chapter 19: Chlorine, Bromine, and Iodine Solid-State NMR

Stephen Wimperis

School of Chemistry and WestCHEM, University of Glasgow, Glasgow G12 8QQ, UK

Chapter 3: Quadrupolar Coupling: An Introduction and Crystallographic AspectsChapter 11: STMAS NMR: Experimental Advances

Gang Wu

Department of Chemistry, Queen’s University, Kingston, ON K7L 3N6, Canada

Chapter 15: Alkali Metal NMR of Biological MoleculesChapter 17: Oxygen-17 NMR Studies of Organic and Biological Molecules

James P. Yesinowski

Chemistry Division, Naval Research Laboratory, Washington, DC 20375-5342, USA

Chapter 24: Quadrupolar NMR of Semiconductors

Josef W. Zwanziger

Department of Chemistry, Dalhousie University, Halifax, NS B3H 4J3, Canada

Chapter 13: Computing Electric Field Gradient Tensors

Series Preface

The Encyclopedia of Nuclear Magnetic Resonance was published in eight volumes in 1996, in part to celebrate the fiftieth anniversary of the first publications in NMR in January 1946. Volume 1 contained an historical overview and ca. 200 short personal articles by prominent NMR practitioners, while the remaining seven volumes comprise ca. 500 articles on a wide variety of topics in NMR (including MRI). Two “spin-off” volumes incorporating the articles on MRI and MRS (together with some new ones) were published in 2000 and a ninth volume was brought out in 2002. In 2006, the decision was taken to publish all the articles electronically (i.e. on the World Wide Web) and this was carried out in 2007. Since then, new articles have been placed on the web every three months and a number of the original articles have been updated. This process is continuing. The overall title has been changed to the Encyclopedia of Magnetic Resonance to allow for future articles on EPR and to accommodate the sensitivities of medical applications.

The existence of this large number of articles, written by experts in various fields, is enabling a new concept to be implemented, namely the publication of a series of printed handbooks on specific areas of NMR and MRI. The chapters of each of these handbooks will comprise a carefully chosen selection of Encyclopedia articles relevant to the area in question. In consultation with the Editorial Board, the handbooks are coherently planned in advance by specially selected editors. New articles are written and existing articles are updated to give appropriate complete coverage of the total area. The handbooks are intended to be of value and interest to research students, postdoctoral fellows, and other researchers learning about the topic in question and undertaking relevant experiments, whether in academia or industry.

Robin K. Harris

University of Durham, Durham, UK

Roderick E. Wasylishen

University of Alberta, Edmonton, Alberta, Canada

November 2009

Volume Preface

In August 1950, the classic paper by R. V. Pound, “Nuclear Electric Quadrupolar Interactions in Crystals”, appeared in Physical Review and opened the door for NMR studies of quadrupolar nuclei in solids. Looking back at this 18-page masterpiece (Phys. Rev., 79, 685–702) one is struck by the numerous theoretical and experimental insights provided by Professor Pound. Apart from discussing the 7Li, 23Na, and 27Al NMR spectra of single crystals of Li2SO4;•H2O, NaNO3, and Al2O3, respectively, powder lineshapes and relaxation effects (including the results of saturating satellite transitions) are provided. Many outstanding papers quickly followed and a 1957 review by M. H. Cohen and F. Reif, published in Solid State Physics—Advances and Applications, summarized the early quadrupolar NMR literature.

Over the next 15 years, many papers dealt with the analysis of quadrupolar NMR powder lineshapes complicated by anisotropic magnetic shielding, dipolar interactions, and so on. A comprehensive review of magnetic resonance lineshapes in polycrystalline solids appeared in 1975 (P. C. Taylor, J. F. Baugher and H. M. Kritz, Chem. Rev., 1975, 75, 203–240). It is interesting to mention that in the section of this review discussing spinning techniques, the following statement appears: “Little has been done with nuclei possessing quadrupole moments. Because the quadrupolar interaction tensor is traceless, spinning the sample will eliminate first-order quadrupolar effects. Second-order effects will remain in a modified form, however, and these could be studied in the absence of dipolar broadening” (two references to E. R. Andrew and coworkers follow). We think it is fair to say that up to this time almost all contributions in the field of quadrupolar NMR of solids had been made by physicists working largely with “home-built equipment”. In the early 1980s, there was an explosion of activity involving NMR studies of quadrupolar nuclei with nonintegral spins in solids using magic angle spinning techniques. Many chemists and chemical physicists (E. Oldfield, A. Samoson, E. Lippmaa, R. K. Harris, C. A. Fyfe and others) were responsible for demonstrating the advantages of magic angle spinning (MAS) for investigating noninteger quadrupolar nuclei in solids. At the same time, the potential of quadrupolar nuclei, in particular 2H, for studying dynamics in solids was demonstrated by several research groups.

It is not the purpose of this preface to present a review of NMR activity involving quadrupolar nuclei in solids; however, it is important to recognize that the pace at which techniques and applications in this area of research has developed in recent years has not subsided. In fact, the number of relevant publications continues to expand. There are several reasons for this trend, including the following: First, the availability of high magnetic field strengths has had an enormous impact on the nature of the problems that one can tackle. In particular, because the second-order quadrupolar interaction scales as the inverse Larmor frequency, the quadrupolar perturbation of the central NMR transition, , decreases at higher fields. Second, there have been considerable technological improvements in producing rotors for sample spinning experiments that spin rapidly, stably, and reliably. As outlined in this handbook, this has led to the development and use of several techniques (e.g., double-rotation (DOR), dynamic-angle spinning (DAS), multiple-quantum magic-angle spinning (MQMAS), satellite transition magic angle spinning (STMAS)). At the same time, commercial vendors of NMR equipment have made available double- and triple-resonance probes capable of MAS in standard-bore magnets. Moreover, improvements in spectrometer hardware and software have provided experimentalists with unprecedented flexibility in designing pulse sequences, and so on. Finally, computers and quantum mechanical techniques for computing electric field gradient tensors, magnetic shielding tensors, and so on for nuclei embedded in crystal lattices as well as in “isolated” molecules are making important contributions to science in this area.

The purpose of the present handbook is to provide under a single cover the fundamental principles, techniques, and applications of quadrupolar NMR as it pertains to solid materials. The chapters herein have been taken from or will appear as individual articles in the Encyclopedia of Magnetic Resonance (both the online and printed versions). Each chapter has been prepared by an expert who has made significant contributions to our understanding and appreciation of the importance of NMR studies of quadrupolar nuclei in solids. The text is divided into three sections: (i) Basic Principles, (ii) Advanced Techniques, and (iii) Applications. The first section provides the reader with the background necessary to appreciate the challenges in acquiring and interpreting NMR spectra of quadrupolar nuclei in solids. The second section presents cutting-edge techniques and methodology for employing these techniques to investigate quadrupolar nuclei in solids. The final section explores applications of solid-state NMR studies of solids ranging from investigations of dynamics, characterizations of biological samples, organic and inorganic materials, porous materials, glasses, catalysts, semiconductors, and high-temperature superconductors.

As mentioned above, the articles can also be found with minimal differences in format in the online Encyclopedia of Magnetic Resonance, at www.wileyonlinelibrary.com/ref/emr. The online versions also include brief autobiographies of the authors, a list of related encyclopedia articles, and in some cases, acknowledgements by the authors. They also have cross-references to encyclopedia articles that are not part of this handbook. Additionally, article abstracts and keywords can be found online.

We hope that readers find the contributions here instructive and that the knowledge acquired advances their research. Also, the related handbooks, NMR Crystallography and Solid-State NMR of Biopolymers should provide complementary information about NMR of solids. Finally, we wish to thank all authors for their contributions to this handbook, and Professor Robin K. Harris for many helpful suggestions. We also thank people at Wiley, particularly Stacey Woods, Elizabeth Grainge and Rosanna Curran, for their efforts, patience in assembling author contributions as well as Martin Rothlisberger for his support and leadership.

Roderick E. Wasylishen

University of Alberta, Edmonton, Canada

Sharon E. Ashbrook

University of St Andrews, St Andrews, UK

Stephen Wimperis

University of Glasgow, UK

June 2012

Abbreviations and Acronyms

1Q

Single-Quantum

2D

Two Dimensional

2QF-COSY

Double-Quantum-Filtered Correlation Spectroscopy

AAG

Ala-Ala-Gly

ABMS

Anisotropy of the Bulk Magnetic Susceptibility

ADF

Amsterdam Density Functional

ADRF

Adiabatic Demagnetization in the Rotating Frame

APW

Augmented Plane Wave Method

ARP

Adiabatic Rapid Passage

BCS

Bardeen–Cooper–Schrieffer

BLEW

Burum, Linder & Ernst (Windowless pulse sequence)

BLYP

Becke, Lee, Yang, Parr

BO

Bridging Oxygen

BOM

Bond Orbital Model

BPP

Bloembergen–Purcell–Pound

BR-24

Burum & Rhim (pulse sequence)

CAS

Crystal Axis System

CB

Conduction Band

CG

Conjugate

CODEX

Centerband-only Detection of Exchange Experiment

COSY

Correlation Spectroscopy

CP

Cross Polarization

CPMAS

Cross Polarization and Magic Angle Spinning

CPMG

Carr–Purcell–Meiboom–Gill

CRAMPS

Combined Rotation and Multiple-Pulse Spectroscopy

CS

Chemical Shift

CSA

Chemical Shift Anisotropy

CST

Chemical Shift Tensor

CT

Central Transition

CT

Contact Time

CTMAS

Central Transition Magic Angle Spinning

CW

Continuous Wave

CYCLOPS

Cyclically Ordered Phase Sequence

D

Dipolar

DAH

Dynamic Angle Hopping

DANTE

Delays Alternating with Nutations for Tailored Excitation

DAS

Dynamic Angle Spinning

DD

Dipole-Dipole

DEAR

Dipolar Exchange-Assisted Recoupling

DEISM

Direct Enhancement of Integer-Spin Magnetization

DEPT

Distortionless Enhancement by Polarization Transfery

DFS

Double Frequency Sweeps

DFT

Density Functional Theory

DMS

Dilute Magnetic Semiconductors

DNP

Dynamic Nuclear Polarization

DOR

Double Rotation

DOS

Density of States

DPPC

Dipalmitoylphosphatidylcholine

DQ

Double-Quantum

DQC

Double-Quantum Coherence

DQF

Double-Quantum Filter

DR-NQR

Double-Resonance Nuclear Quadrupole Resonance

DRSE

Dipolar-Rotational Spin Echoes

DSPC

Distearoyl-sn-glycero-3 phosphatidylcholine

EFG

Electric Field Gradient

ENDOR

Electron-Nucleus Double Resonance

EPR

Electron Paramagnetic Resonance

ESR

Electron Spin Resonance

EXAFS

Extended X-Ray Absorption Fine Structure