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Vibrational Optical Activity Vibrational Optical Activity Principles and Applications LAURENCE A. NAFIE Department of Chemistry, Syracuse University Syracuse, New York, 13244-4100, USA This edition first published 2011 2011 John Wiley & Sons Ltd. Registered office John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom Fordetails of ourglobal editorial offices,for customer services and for information about how to apply for permission to reuse the copyright material in this book please see our website at www.wiley.com. The right of the author to be identified as the author of this work has been asserted in accordance with the Copyright, Designs and Patents Act 1988. All rights reserved. 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In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to the use of experimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert or instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in the instructions or indication of usage and for added warnings and precautions. The fact that an organization or Website is referred to in this work as a citation and/or a potential source of further information does not mean that the author or the publisher endorses the information the organization or Website may provide or recommendations it may make. Further, readers should be aware that InternetWebsiteslistedinthisworkmayhavechangedordisappearedbetweenwhenthisworkwaswrittenandwhenit isread.Nowarrantymaybecreatedorextendedbyanypromotionalstatementsforthiswork.Neitherthepublishernor the author shall be liable for any damages arising herefrom. Library of Congress Cataloging-in-Publication Data Nafie, Laurence A. Vibrational optical activity : principles and applications / Laurence A. Nafie. p. cm. Includes bibliographical references and index. ISBN 978-0-470-03248-0 (cloth) 1. Vibrational spectra. I. Title. QC454.V5N34 2011 539.6–dc22 2011012255 A catalogue record for this book is available from the British Library. Print ISBN: 9780470032480 ePDF ISBN: 9781119976509 oBook ISBN: 9781119976516 ePub ISBN: 9781119977537 Mobi: 9781119977544 Set in 9/11pt Times by Thomson Digital, Noida, India This book is dedicated to the loving, nurturing, and inspiring support of both my parents, Marvin Daniel and Edith Fletcher Nafie and my mother’s parents Frederic Stark and Edith Webster Fletcher, and to my loving wife Rina Dukor who, for the last 15 years, has been my business and scientific partner in helping me to bring vibrational optical activity to the world, and who recently became, as well, my life’s partner in marriage. Contents Preface xvii 1 Overview of Vibrational Optical Activity 1 1.1 Introduction to Vibrational Optical Activity 1 1.1.1 Field of Vibrational Optical Activity 1 1.1.2 Definition of Vibrational Circular Dichroism 3 1.1.3 Definition of Vibrational Raman Optical Activity 5 1.1.4 Unique Attributes of Vibrational Optical Activity 7 VOA is the Richest Structural Probe of Molecular Chirality 7 VOA is the Most Structurally Sensitive Form of Vibrational Spectroscopy 8 VOA Can be Used to Determine Unambiguously the Absolute Configuration of a Chiral Molecule 8 VOA Spectra Can be Used to Determine the Solution-State Conformer Populations 8 VOA Can be Used to Determine the ee of Multiple Chiral Species of Changing Absolute and Relative Concentration 8 1.2 Origin and Discovery of Vibrational Optical Activity 9 1.2.1 Early Attempts to Measure VOA 9 1.2.2 Theoretical Predictions of VCD 10 1.2.3 Theoretical Predictions of ROA 11 1.2.4 Discovery and Confirmation of ROA 11 1.2.5 Discovery and Confirmation of VCD 13 1.3 VCD Instrumentation Development 14 1.3.1 First VCD Measurements – Dispersive, Hydrogen-Stretching Region 14 1.3.2 Near-IR VCD Measurements 14 1.3.3 Mid-IR VCD Measurements 15 1.3.4 Fourier Transform VCD Instrumentation 15 1.3.5 Commercially Available VCD Instrumentation 15 1.4 ROA Instrumentation Development 16 1.4.1 First ROA Measurements – Single Channel ICP-ROA 16 1.4.2 Multi-Channel ROA Measurements 17 1.4.3 Backscattering ROA Measurements 17 1.4.4 SCP-ROA Measurements 17 1.4.5 DCP-ROA Measurements 18 1.4.6 Commercially Available ROA Instruments 18 ... - tailieumienphi.vn
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