Spectra of Atoms and Molecules

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Spectra of Atoms and Molecules
Second Edition

Peter F. Bernath

OXFORD
UNIVERSITY PRESS

2005
OXJORD
UNIVERSITY PRESS

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Library of Congress Cataloging-in-Publication Data
Bernath, Peter F.
Spectra of atoms and molecules / Peter F. Bernath.—2nd ed.
p. cm.
Includes bibliographical references and index.
ISBN-13 978-0-19-517759-6
ISBN 0-19-517759-2
1. Spectrum analysis—Textbooks. 2. Atomic spectroscopy.
3. Molecular spectroscopy. I. Title.
QC451.B47 2005
535.8'4—dc22 2004062020

9 8 7 6 5 4 3 2 1
Printed in the United States of America
on acid-free paper
For Robin, Elizabeth, and Victoria
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Preface

In this second edition I have mainly updated and revised the material presented in the
first edition. For example, the 1998 revision of the physical constants has been used
throughout, and the use of symbols and units conforms more closely to recommended
practice. The level of treatment and spirit of the book have not changed. I still aim
to meet the needs of new students of spectroscopy regardless of their background. I
have restrained myself and have not introduced spherical tensors, for example, because
I believe that too many new concepts at one time are confusing.
A certain amount of new material has been added based on my recent experiences
with what is misleadingly called "quantitative spectroscopy." Spectroscopists are gen-
erally divided into two camps: those who interpret the spectral positions of lines and
bands, and those who concern themselves more with line and band intensities. The
latter camp is populated mainly by analytical chemists, but includes astronomers and
atmospheric scientists as well.
Nothing in spectroscopy causes as much confusion as line intensities. Some of the
problems seem to originate from the degeneracies inherent in atomic and molecular
systems. The usual intensity formulas are derived (as in Chapter 1) for transitions
between nondegenerate quantum states, while measurements are generally made on
transitions between degenerate energy levels. The correct inclusion of this degeneracy
turns out to be a nontrivial problem and is presented in Chapter 5 for atoms, but the
expressions given there also apply to molecular systems. Even the definition of what
constitutes a line can be a source of difficulties.
Line intensities are also confusing because of the dozens of different units used to
report line and band strengths. The best procedure is to derive and cite all formulas
in SI units, and then make any needed conversions to "customary" units in a second
step. It is surprisingly difficult to locate line intensity formulas in SI units, with the
appropriate degeneracies included. The line intensity formulas listed in this book should
prove useful to the modern student.
Other than the addition of material pertaining to line intensities in Chapters 5 to
10, a major change in the second edition is in the discussion of the Raman effect and
light scattering (Chapter 8). The standard theoretical treatment of light scattering and
the Raman effect, as first presented by Placzek in the 1930s, has been added. Although
Placzek's approach is hardly light reading, the diligent student will find the derivations
illuminating. A solid understanding of the classical and quantum mechanical theory of
polarizability of molecules is indispensable in the area of nonlinear spectroscopy.
I am very grateful for the comments and helpful criticism from many people, partic-
ularly F. R. McCourt, R. J. Le Roy, C. Bissonette, K. Lehmann, A. Anderson, R. Shiell,
and J. Hardwick. I also thank my fall 2004 graduate class in molecular spectroscopy

vii
Vlll

(M. Dick, D. Fu, S. Gunal, T. Peng, and S. Yu) for their comments and corrections.
The figures for the second edition have been prepared by S. M. McLeod, T. Nguyen,
Y. Bresler, and E. R. Bernath.
Finally, my wife Robin has made the second edition possible through her continuing
encouragement and understanding. My special thanks to her.

Ontario P.F.B.
August 2004