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Academic Press is an imprint of Elsevier The Boulevard, Langford Lane, Kidlington, Oxford, OX51GB, UK 32 Jamestown Road, London NW1 7BY, UK Radarweg 29, PO Box 211, 1000 AE Amsterdam, The Netherlands 225 Wyman Street, Waltham, MA 02451, USA 525 B Street, Suite 1900, San Diego, CA 92101-4495, USA First edition 2012 Copyright © 2012 Elsevier Ltd. All rights reserved No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means electronic, mechanical, photocopying, recording or otherwise without the prior written permission of the publisher Permissions may be sought directly from Elsevier’s Science & Technology Rights Department in Oxford, UK: phone (+44) (0) 1865 843830; fax (+44) (0) 1865 853333; email: [email protected]. Alternatively you can submit your request online by visiting the Elsevier web site at http://elsevier.com/locate/permissions, and selecting Obtaining permission to use Elsevier material Notice No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein. Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drug dosages should be made British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress ISBN: 978-0-12-397020-6 ISSN: 0066-4103 For information on all Academic Press publications visit our website at store.elsevier.com Printed and bound in Great Britain 12 13 14 11 10 9 8 7 6 5 4 3 2 1 CONTRIBUTORS Ruud L.E.G. Aspers Radboud University, Institute for Molecules and Materials, Biophysical Chemistry, Heyendaalseweg, Nijmegen, The Netherlands Bruce J. Balcom MRI Research Centre, Department of Physics, and Department of Chemistry, University of New Brunswick, P.O. Box 4400, Fredericton, New Brunswick, Canada Teresa Blasco Instituto de Tecnologı´a Quı´mica (UPV-CSIC), Universidad Polite´cnica de Valencia-Consejo Superior de Investigaciones Cientı´ficas, Avda. de los Naranjos, s/n, Valencia, Spain Angel C. de Dios Department of Chemistry, Georgetown University, Washington, DC, USA Martin Jaeger DSM Nutritional Products Ltd., Analytical Research Center, Wurmisweg, Kaiseraugst, Switzerland Cynthia J. Jameson Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois, USA Luı´s Mafra Department of Chemistry, CICECO, University of Aveiro, Aveiro, Portugal, and Departamentos de Quı´mica Fı´sica y Analı´tica y Quı´mica Orga´nica e Inorga´nica, Universidad de Oviedo, Oviedo, Spain Colleen E. Muir MRI Research Centre, Department of Physics, and Department of Chemistry, University of New Brunswick, P.O. Box 4400, Fredericton, New Brunswick, Canada Jose´ Alejandro Vidal-Moya Instituto de Tecnologı´a Quı´mica (UPV-CSIC), Universidad Polite´cnica de Valencia-Consejo Superior de Investigaciones Cientı´ficas, Avda. de los Naranjos, s/n, Valencia, Spain vii PREFACE As is usual in this series of reports, Volume 77 of Annual Reports on NMR Spectroscopy consists of accounts of recent progress in several areas of molec- ular science. The volume commences with a discussion of ‘Recent Advances in Nuclear Shielding Calculations’ by A. C. de Dios and C. J. Jameson; this is followed by a review of ‘Pure Phase Encode Magnetic Resonance Imaging of Fluids in Porous Media’ by C. E. Muir and B. J. Balcom; M. Jaeger and R. L. E. G. Aspers report on ‘Steroids and NMR’; the final chapter, by L. Mafra, J. A. Vidal-Moya and T. Blasco, covers ‘Structural Characteriza- tion of Zeolites by Advanced Methods of Solid State NMR Spectroscopy’. It is a great pleasure for me to thank all of the contributors for their timely and significant contributions. G. A. WEBB Royal Society of Chemistry Burlington House Piccadilly London UK ix CHAPTER ONE Recent Advances in Nuclear Shielding Calculations Angel C. de Dios* , Cynthia J. Jameson† *Department of Chemistry, Georgetown University, Washington, DC, USA †Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois, USA Contents 1. Overview of This Review 4 2. Advances in Methods of Calculation 5 2.1 Relativistic calculations 5 2.2 Density functional calculations 11 3. Local Effects on Shielding: Single Molecules, Clusters, and Fragments 15 3.1 Conformational effects 16 3.2 Neighbouring non-bonded atom effects 16 3.3 Hydrogen-bonding effects 18 3.4 Electrostatic field effects 19 3.5 Intermolecular relativistic effects 22 3.6 Shielding and chirality 23 4. Shielding in Extended Networks 25 4.1 Approaches to extended networks 25 4.2 Crystalline materials 32 4.3 Non-crystalline materials, glasses 34 4.4 NICS in periodic systems 36 4.5 Relativistic calculations in solids 36 4.6 The case for retaining cluster approaches in our toolbox 37 5. Dynamic Averaging of Shielding 42 5.1 Why is averaging so important for nuclear shielding calculations? 42 5.2 Rovibrational averaging 43 5.3 Dynamic averaging in condensed phases 45 6. Extracting Information from NMR Chemical Shifts with the Help of Theoretical Calculations 54 6.1 Shielding tensors as tools for NMR crystallography 55 6.2 Details of local structure 57 6.3 Shielding as a probe for intermolecular interactions 59 6.4 Characterization of solids 60 References 61 Annual Reports on NMR Spectroscopy, Volume 77 # 2012 Elsevier Ltd. 1 ISSN 0066-4103 All rights reserved. http://dx.doi.org/10.1016/B978-0-12-397020-6.00001-5 2 Angel C. de Dios and Cynthia J. Jameson Abstract Nuclear magnetic shielding calculations have reached a great deal of sophistication, as these now incorporate both relativistic and correlation effects. Approaches now include molecular dynamics as well as effects of the medium in condensed phases. With these computational tools, calculated shielding values are now obtained under conditions as close as possible to those of a sample inside a nuclear magnetic resonance spectrom- eter. Indeed, computations are approaching the limits of experimental uncertainty. A brief description of new methodologies of shielding calculations is presented followed by a review of the various factors that may influence shielding. The usefulness of being able to reproduce experimental data is highlighted by citing how shielding calculations in many instances have enabled avenues for extracting information on various systems. Key Words: Absolute shielding, Chemical shifts, Chirality, Cluster models, Conforma- tional dependence, Density functional theory, Disorder in crystals, Electron correlation, Four-component calculations, Gas phase NMR, Hydrogen bonds, Intra- and inter- molecular effects, Isotope shifts, Medium effects, Molecular dynamics, NMR crystallog- raphy, Non-bonded interactions, Periodic boundary calculations, Polarizable continuum model, Polymorphs, Pseudopotentials, Relativistic calculations, Rovibrational averaging, Shielding surfaces, Structure determination, Temperature dependence, Tensor, Torsion angles, Two-component calculations ABBREVIATIONS AE all-electron BO Born–Oppenheimer BPPT Breit Pauli perturbation theory CCSD coupled cluster singles and doubles CFP charge field perturbation CI configuration interaction COSMO conductor-like screening model CPMD Car-Parinello molecular dynamics CSGT continuous set of gauge transformation DFT density functional theory DHF Dirac–Hartree–Fock ECP effective core potential EIM embedded ion method EPR electron paramagnetic resonance GAPW Gaussian and augmented plane-wave method GGA generalized gradient approximation GIAO gauge-including atomic orbitals GIPAW gauge-including projector augmented wave HAHA heavy atom heavy atom HALA heavy atom light atom HF Hartree–Fock HOMO highest occupied molecular orbital IGAIM individual gauge for atoms in molecules Recent Advances in Nuclear Shielding Calculations 3 KS Kohn–Sham LAPW linear-augmented plane waves LDA local density approximation LHF-CEDA localized Hartree-Fock-common energy denominator Green’s function approximation LLH localized local hybrid LMF local mixing function LR-ESC linear response elimination of small component LUMO lowest occupied molecular orbital MAS magic angle spinning MB-GIAO magnetically balanced gauge-including atomic orbitals MC Monte Carlo MD molecular dynamics MM molecular mechanics NAO numeric atomic orbital NBO natural bond orbital NICS nucleus independent chemical shift NMR nuclear magnetic resonance OEP optimized effective potential OOD occupied-orbital dependent PAW projector augmented wave PBC periodic boundary conditions PCM polarizable continuum model PES potential energy surface PW plane wave QM quantum mechanics RMB restricted magnetic balance RPA random phase approximation RSC relativistic small core SCF self-consistent field SCREEP surface charge representation of the electrostatic embedding potential SO spin–orbit SPARTA shift prediction from analogy in residue type and torsion angle SPC simple point charge SSNMR solid-state nuclear magnetic resonance STO Slater-type orbitals SWNT single-walled nanotube USPP ultrasoft pseudopotential XC exchange correlation XRD X-ray diffraction ZORA zeroth-order regular approximation 4 Angel C. de Dios and Cynthia J. Jameson 1. OVERVIEW OF THIS REVIEW Monographs on shielding calculations have traced the advances in this field over the years: Nuclear Magnetic Shieldings