Fundamentals of Molecular Spectroscopy: Fourth Edition

FUNDAMENTALS
OF MOLECULAR
SPECTROSCOPY
FOURTH EDITION
COLIN N. BANWELL AND ELAINE Ma McCASH

FUNDAMENTALS OF MOLECULAR SPECTROSCOPY
FUNDAMENTALS OF
MOLECULAR SPECTROSCOPY
Fourth Edition
Colin N. Banwell
TessP France
Elaine M. McCash
Department of Chemistry
University of York
The McGraw-Hill Companies

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British Library Cataloguing in Publication Data

Banwell. C. N.
Fundamentals of Molecular Spectroscopy.
4Rev.ed
I. Title 11. McCash, Elaine
535.84
ISBN M7-707976-0
Library of Congress Cataloging-in-Publication Data

Banwell, C. N.
Fundamentals of molecular spectroscopy / Colin Banwell, Elaine
McCash. - 4th ed.
p. cm.
Includes bibliographical references and index.
ISBN M 7 - 7 0 7 9 7 6 0
1. Molecular spectroscopy. I . McCash, Elaine
11. Title.
QD96.M65B36 1994
543'.08586c20 94869
CIP
McGraw -Hill
A Division of TheMcCmw.Hill Compmues
E
Copyright 0 1994 McGraw-Hill International (UK) Limited.
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
permission of McGraw-Hill International (UK) Limited.
345 CUP 1098
Typeset by Keyword Publishing Services, London

and printed and bound in Great Britain at the University Press, Cambridge
Printed on permanent paper in compliance with IS0 Standard 9706
To
Professor Norman Sheppard, FRS
for bringing together the partnership which produced this volume,
and for his great influence on the teaching and practice of chemical spectroscopy
over a period of some forty years.
CONTENTS
PREFACE
CHAPTER 1 INTRODUCTION
1.1 Characterization of Electromagnetic Radiation
1.2 The Quantization of Energy
1.3 Regions of the Spectrum
1.4 Representation of Spectra
1.5 Basic Elements of Practical Spectroscopy
1.6 Signal-to-noise: Resolving Power
1.7 The Width and Intensity of Spectral Transitions
1.8 Fourier Transform Spectroscopy
1.9 Enhancement of Spectra: Computer Averaging
1.10 Stimulated Emission: Lasers
1.11 Synchrotron Radiation
Bibliography
Problems
CHAPTER 2 MICROWAVE SPECTROSCOPY

2.1 The Rotation of Molecules
2.2 Rotational Spectra
2.3 Diatomic Molecules
2.4 Polyatomic Molecules
2.5 Techniques and Instrumentation
2.6 Chemical Analysis by Microwave Spectroscopy
2.7 The Microwave Oven
Bibliography
Problems
CHAPTER 3 INFRA-RED SPECTROSCOPY

3.1 The Vibrating Diatomic Molecule
3.2 The Diatomic Vibrating Rotator
viii CONTENTS
The Vibration-Rotation Spectrum of Carbon Monoxide

Breakdown of the Born-Oppenheimer Approximation: The
Interaction of Rotations and Vibrations
The Vibrations of Polyatomic Molecules
The Influence of Rotation on the Spectra of Polyatomic
Molecules
Analysis by Infra-red Techniques
Techniques and Instrumentation
Bibliography
Problems
CHAPTER 4 RAMAN SPECTROSCOPY

4.1 Introduction
4.2 Pure Rotational Raman Spectra
4.3 Vibrational Raman Spectra
4.4 Polarization of Light and the Raman Effect
4.5 Structure Determination from Raman and Infra-red
Spectroscopy
4.7 Near Infra-red FT-Raman Spectroscopy
Bibliography
Problems
CHAPTER 5 ELECTRONIC SPECTROSCOPY OF ATOMS

5.1 The Structure of Atoms
5.2 Electronic Angular Momentum
5.3 Many-Electron Atoms
5.4 The Angular Momentum of Many-Electron Atoms
5.5 Photoelectron Spectroscopy
5.6 The Zeeman Effect
5.7 The Influence of Nuclear Spin
5.8 Conclusion
Bibliography
Problems
CHAPTER 6 ELECTRONIC SPECTROSCOPY OF MOLECULES

6.1 Electronic Spectra of Diatomic Molecules
6.2 Electronic Structure of Diatomic Molecules
6.3 Electronic Spectra of Polyatomic Molecules
6.5 Molecular Photoelectron Spectroscopy
Bibliography
Problems
CHAPTER 7 SPIN RESONANCE SPECTROSCOPY

7.1 Spin and an Applied Field
7.2 Nuclear Magnetic Resonance Spectroscopy: Hydrogen Nuclei
7.3 Nuclear Magnetic Resonance Spectroscopy: Nuclei Other Than
Hydrogen

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FUNDAMENTALS

COLIN N. BANWELL AND ELAINE Ma McCASH

The McGraw-Hill Companies

British Library Cataloguing in Publication Data

Library of Congress Cataloging-in-Publication Data

345 CUP 1098

Typeset by Keyword Publishing Services, London

CHAPTER 2 MICROWAVE SPECTROSCOPY

CHAPTER 3 INFRA-RED SPECTROSCOPY

The Vibration-Rotation Spectrum of Carbon Monoxide

CHAPTER 4 RAMAN SPECTROSCOPY

CHAPTER 5 ELECTRONIC SPECTROSCOPY OF ATOMS

CHAPTER 6 ELECTRONIC SPECTROSCOPY OF MOLECULES

CHAPTER 7 SPIN RESONANCE SPECTROSCOPY

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