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.
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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
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.
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
126.96.36.199 VOA is the Richest Structural Probe of Molecular
Chirality 7 188.8.131.52 VOA is the Most Structurally Sensitive Form of
Vibrational Spectroscopy 8 184.108.40.206 VOA Can be Used to Determine Unambiguously the
Absolute Conﬁguration of a Chiral Molecule 8 220.127.116.11 VOA Spectra Can be Used to Determine the Solution-State
Conformer Populations 8 18.104.22.168 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
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