NMR Basic Principles and Progress 34 Editors,: P. Diehl E. Fluck H. Gunther R. Kosfeld J. Seelig Guest-Editors: E. Fluck, H. Gunther 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
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Spin-l NMR By N. Chandrakumar Guest-Editors: E. Fluck and H. Gunther With 68 Figures and 2 Tables, Springer
Dr. Narayanan Chandrakumar Central Leather Research Institute Adayaru, 600 020 Madras, Tamil Nadu I India ISBN-13: 978-3-642-64689-8 e-isbn-13: 978-3-642-61089-9 DOT: 10.1007/978-3-642-61089-9 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereofis permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer Verlag. Violations are liable for prosecution under the German Copyright Law. Springer-Verlag Berlin Heidelberg 1996 Library of Congress Catalog Card Number 93-9522 Softcover reprint of the hardcover 1 st edition 1996 The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Product liability: The publishers cannot guarantee the accuracy of any information about dosage and application contained in this book. In every individual case the user must check such information by consulting the relevant literature. Typesetting: Thomson Press (India) Ltd, New Delhi Offsetprinting: Saladruck, Berlin; Bookbinding: LOderitz & Bauer, Berlin SPIN: 10474251 5113020-5432 I 0 - Printed on acid-free paper
Guest-Editors Prof. Dr. Dr. h.c. Ekkehard Fluck Gmelin-Institut, VarrentrappstraBe 40-42, 60486 Frankfurt, FRG Prof. Dr. Harald GUnther Universitat Siegen, Organische Chemie II, HolderlinstraBe 3, 57076 Siegen, FRG Editorial Board: Prof. Dr. Peter Diehl Prof. Dr. Ekkehard Fluck Prof. Dr. H. Gunther Prof. Dr. Robert Kosfeld Prof. Dr. J. Seelig Institut flir Physik der Universitlit Basel, KlingelbergstraBe 82, CH-4056 Basel Gmelin-Institut, VarrentrappstraBe40/42, 0-60486 Frankfurt am Main, FRG Universitat Siegen, Organische Chemie n, Postfach 101240,0-57076 Siegen, FRG In den Atzenbenden 30, 0-52080 Aachen, FRG Biozenbum der Universitat Basel, Abt. Biophysikalische Chemie, K1ingelbergstra6e 70, CH-4056 Basel Advisory Board: Prof. Dr. Geoffrey Bodenhausen Prof. Dr. Sturse Forsen Prof. Dr. Robin K. Harris Prof. Dr. C. L. Khetrapal Prof. Dr. T. E. Lippmaa Prof. Dr. G. J. Marlin Prof. Dr. Harry Pfeifer Prof. Dr. Alex Pines Prof. Dr. Bernard L. Shapiro Section de cbimie, Universite de Lausanne, Rue de labarre 2, CH-I005 Lausanne Departmeut ofphysical Chemistry, Chemical Centre, University oflund,p.o.b. 740, S-22007 Lund University of Durham, Departmeut of Chemistry, Science Laboratories, South Road, GB-Durham DHI 3LE Sophisticated Insbuments Facility, Indian Institute of Science, Bangalore-560 01 2, India Institute of Chemical Physics and Biophysics, Academy of Sciences of the Estonian SSR, Lenini paiestee 10, Tallinn 20000 I, Estonia Universite de Nantes, U.E.R. de Chimie, ResonanceMagnetiqueNucleaireetReactiviteChimique, UA-CNRS No 472, 2, rue de lahoussiniere, F-440n Nantes Cedex F achbereich Physik, UniversitatLeipzig, Linnestra6e 5, 0-04103 Leipzig,FRG University of California, Berkeley, Department of Chemistry, Berkeley, CA 94720, USA 966 Elsinore Court, Palo Alto, CA 94303, USA
Table of Contents 1 The Basic Physics of Spin-l Systems...... 3 1.1 General Introduction........... 3 1.2 Spin States and Matrix Representations of Operators for Spin-1 5 1.3 Spin-1 Operator Algebra......... 7 1.4 L6wdin Projectors for Spin-1...... 12 1.5 Interactions Relevant in Spin-1 NMR. 12 1.6 Pulse Rotations....... 13 1.7 Density Matrix Description of the State of Spin-1 Ensembles. 14 1.8 Evolution of the Spin-1 System Under Quadrupolar Coupling. 16 1.9 Phase Changes of Spin-1 Wavefunctions Under Rotation.... 16 1.10 Evolution of the Spin-1-Spin-1/2 System Under Scalar Coupling 18 1.11 Spin Tickling in a Spin-1/2-Spin-1 Scalar Coupled System... 21 1.12 Evolution of the Spin-1-Spin-1 System Under Scalar Coupling. 22 1.13 Coherence Transfer Function for Spin-1 Systems. 23 1.14 Quadrupolar Relaxation........... 24 1.15 Spin-1 Behavior of Two Equivalent Spins-1/2... 26 2 NMR of Systems Involving Spin-l Nuclei in the Isotropic Phase. 27 2.1 Chemical Shift Information................... 27 2.2 General Spectral Features Consequent on Coupling to Spin-1 28 2.3 Laboratory Frame Polarization Transfer Involving Spin-1 Nuclei 30 2.4 INEPT Polarization Transfer from Spin-1 (S) to Spin-1/2 (I) 30 2.5 DEPT Polarization Transfer from Spin-1 (S) to Spin-1/2 (I)... 35 2.6 Polarization Transfer from Spin-1/2 (I) to Spin-1 (S)....... 37 2.7 Pulse Width Calibration for Polarization Transfer Experiments 37 2.8 Polarization Transfer Between Spin-1 Nuclei....... 38 2.9 Two-Dimensional Experiments Involving Spin-1 Nuclei 42 2.10 Correlation Spectroscopy (COSY).......... 42 2.11 Heteronuclear Multiple Quantum Spectroscopy. 43 2.12 Homonuclear Multiple Quantum Spectroscopy.. 47 2.13 Relayed Correlation Spectroscopy.......... 53 2.14 Instrumentation for High Resolution Spin-1 NMR 58
viii Table of Contents 3 NMR of Spin-l Systems in the Solid State. 59 3.1 Introduction... 59 3.2 Quadrupolar Echo........................ 62 3.3 leener-broekaert Sequence.................... 64 3.4 Deuterium NMR Spectroscopy of Single Crystal Systems.. 65 3.5 Two-Dimensional Deuterium COSY Spectra in the Solid State. 68 3.6 Deuterium NMR Under Magic Angle Spinning. 68 3.7 Double Quantum Spectroscopy. 68 3.8 QUADSHIFT Experiment..... 78 3.9 Overtone Spectroscopy....... 82 3.10 Spin-l/2-Spin-1 Dipolar Coupling 91 3.11 Spin Alignment............ 96 3.12 Deuterium Exchange Spectroscopy in Single Crystals 97 3.13 Deuterium Exchange Spectroscopy... 98 3.14 Spin-1 Double Quantum Imaging.... 105 3.15 Instrumentation for Solid State NMR. 109 4 References......................... 114