Table Of ContentMatrix Isolation Spectroscopy
NATO ADVANCED STUDY INSTITUTES SERIES
Proceedings of the Advanced Study Institute Programme, which aims
at the dissemination of advanced knowledge and
the formation of contacts among scientists from dIfferent countries
The series is published by an international board of publishers in conjunction
with NATO Scientific Affairs Division
A Life Sciences Plenum Publishing Corporation
B Physics London and New York
C Mathematical and D. Reidel Publishing Company
Physical Sciences Dordrecht, Boston and London
D Behavioural and Sijthoff & Noordhoff International
Social Sciences Publishers
E Applied Sciences Alphen aan den Rijn and Germantown
U.S.A.
Series C - Mathematical and Physical Sciences
Volume 76 - Matrix Isolation Spectroscopy
Matrix Isolation
Spectroscopy
A book based on the lectures given and the discussions
that took place at the NATO Advanced Study Institute held
at the Universite des Sciences et Techniques du Languedoc,
Montpellier, France, July 17-31,1980
edited by
A. 1. BARNES and W. 1. ORVILLE-THOMAS
University of Salford, Department of Chemistry, Salford, England
A. MULLER
Universitti't Bielefeld, Lehrstuhl fur Anorganische Chemie, Bielefeld, West Germany
and
,
R. GAUFRES
Laboratoire de Spectroscopie Mo/eculaire, U.S.T.L., Montpellier, France
D. Reidel Publishing Company
Dordrecht : Holland / Boston: U.S.A. / London: England
Publi~hed in cooperation with NATO Scientific' Affairs Division
Library of Congress Cataloging in Publication Data
Main entry under title:
Matrix isolation spectroscopy.
(NATO Advanced Study Institutes Series. Series C, Mathematical and
Physical Sciences; v. 76)
Includes indexes.
1. Matrix isolation spectroscopy.congresses. I. Barnes, Austin.
II. NATO Advanced Study Institute. III. Series.
QC454.M32M37 1981 543'.0858 81-11972
AACR2
ISBN-I3: 978-94-009-8542-1 e-ISBN-I3: 978-94-009-8540-7
DOl: 10.1007/978-94-009-8540-7
Published by D. Reidel Publishing Company
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Copyright © 1981 by D. Reidel Publishing Company, Dordrecht, Holland
Softcover reprint of the hardcover I st edition 1981
No part of the material protected by this copyright notice may be reproduced or utilized
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without written permission from the copyright owner
CONTENTS
PREFACE ix
Chapter 1. The history of matrix isolation spectroscopy. 1
W.J. Orville-Thomas
SECTION A - TECHNIQUES
Chapter 2. Infrared and Raman matrix isolation 13
spectroscopy.
A.J. Barnes
Chapter 3. Electronic spectroscopy of matrix isolated 27
solutes.
A.J. Rest
Chapter 4. Magnetic circular dichroism - matrix isolation 49
spectroscopy.
R. Grinter
Chapter 5. Electron spin resonance studies of radicals 69
trapped in rare-gas matrices.
M.C.R. Symons
Chapter 6. Mossbauer spectroscopy on matrix-isolated 91
species.
H. Micklitz
Chapter 7. Time and frequency resolved vibrational 129
spectroscopy of matrix isolated molecules:
Population and phase relaxation processes.
H. Dubost
Chapter 8. Stable molecules. 173
J.J. Turner
Chapter 9. Generation and trapping of unstable solutes 187
in low temperature matrices.
A.J. Rest
vi CONTENTS
Chapter 10. The characterisation of high temperature 207
molecules using matrix isolation and
vibrational spectroscopy.
J.S. Ogden
Chapter 11. High pressure studies. 231
H. Vu
Chapter 12. Non-traditional matrix isolation: adducts. 265
J.J. Blaha, C.E. Meloan and W.G. Fateley
SECTION B - MATRIX EFFECTS
Chapter 13. Interpretation of infrared and Raman spectra 275
of trapped molecular impurities from interaction
potential calculations.
C. Girardet and D. Maillard
Chapter 14. Matrix induced changes in the electronic 347
spectra of isolated atoms and molecules.
D.M.Kolb and F. Forstmann
Chapter 15. Matrix effects studied by electron spin 369
resonance spectroscopy.
M.C .R. Symons
Chapter 16. Molecular motion in matrices. 397
J.R. Durig and J.F. Sulli.van
Chapter 17. Vibrational band intensities in matrices. 415
W.B. Person
SECTION C - APPLICATIONS
Chapter 18. Matrix isolation spectroscopy of metal atoms 447
and small clusters.
D.M. Kolb
Chapter 19. Vibrational spectra of matrix isolated 473
gaseous ternary oxides.
M. Spoliti
Chapter 20. Matrix isolation spectra (IR, Ra~n) of 485
transition metal compounds.
A. MUller and R. Jostes
Chapter 21. Metal carbonyls - structure, photochemistry, 495
and IR lasers.
J.J. Turner
CONTENTS vii
Chapter 22. Matrix isolation vibrational spectroscopy 517
on organic molecules.
B.J. van der Veken
Chapter 23. Conformational isomerism studied by matrix 531
isolation vibrational spectroscopy.
A.J. Barnes
Chapter 24. Hydrogen bonding in matrices. 551
J.P. Perchard
Author Index 565
Subject Index 591
PREFACE
The matrix isolation (MI) method has now been used for
nearly thirty years. During this period it has been actively
developed and the range of problems tackled greatly extended.
Originally it was used for studies of transient species involv-
ing vibrational, electronic and ESR spectroscopy. Nowadays the
study of transient species forms a comparatively small part of
HI work since it has been amply demonstrated that very fruitful
information can be obtained of the structure and interactions of
stable molecules and their aggregates.
In addition to the s~ectroscopic methods mentioned above the
MI technique is nowadays a standard method in research based on
vibrational relaxation, luminescence, Mossbauer, magnetic circular
dichroism, pulsed NMR and photoelectron spectroscopy.
The matrix isolation technique affords considerable
advantages over more conventional methods in most applications of
spectroscopy. Areas where the technique has been widely applied,
or shows great potential, include: metal atom chemistry, and its
relation to surface chemistry, high temperature inorganic species,
transition metal complexes, interstellar species, free radicals
and unstable molecules, conformational studies, molecular com-
plexes, and intermolecular forces.
Many of these applications have been tackled using more than
one of the techniques listed above, but usually in different
laboratories. There are a variety of specialised problems
associated with the matrix technique, known generally as matrix
effects. The International Conference on Matrix Isolation
Spectroscopy, held in West Berlin in 1977, highlighted the
lack of communication between different hranches of matrix
isolation spectroscopy and demonstrated the enormous value of
such cross-fertilisation in solving problems and extracting the
maximum benefits from the matrix technique. This was, of course,
a conference of active research workers in matrix isolation.
This book is based on the lectures given and the discussions
that took place at the NATO-AS I on Matrix Isolation Spectroscopy
ix
A. J. Barnes et al. (eds.), Matrix Isolation Spectroscopy, ix-x.
Copyright © 1981 by D. Reidel Publishing Company.
x PREFACE
that took place at the Universite des Sciences et Techniques du
Languedoc, Montpellier, France, July 1980. The contents are so
organised that young research workers can be made to realise the
potential, not only of the matrix technique, but also of
utilising as many different spectroscopic tools as possible.
The authors were selected on the basis that as many as possible
worked with more than one type of spectroscopy. The text is
organised so that the main topics are introduced, the experimental
techniques are outlined and the theory developed. In this way
the readers will acquire the background necessary as an
introduction to problem solving.
We are grateful to the authors for expanding their lecture
notes into the authoritative accounts found in this book. Our
thanks are also due to those who gave permission for the
reproduction of various figures. Finally we thank the NATO
Scientific Affairs Division for their sponsorship without which
the Advanced Study Institute could not have been held.
A.J. Barnes
R. Gaufres
A. MUller
W.J. Orville-Thomas
CHAPTER 1: THE HISTORY OF MATRIX ISOLATION SPECTROSCOPY
W.J. ORVILLE-THOMAS
Department of Chemistry and Applied Chemistry, University
of Salford, Salford, U.K.
1.1 INTRODUCTION
1.2 BASIC EQUIPMENT
1.3 EXPERIMENTAL METHODS
1.4 PROPERTIES OF MATRICES
1.S MATRIX ISOLATION SPECTROSCOPY AND APPLICATIONS
1.1 INTRODUCTION
The use of low temperature as a controlling factor in
chemical experiments is wide spread. All undergraduates are
familiar with the use of slush baths or liquid nitrogen as
important tools for certain chemical operations. For
spectroscopists, however, the possibility of being able to cool
samples under highly controlled conditions has added an entirely
new dimension to research possibilities. Using cryogenic
techniques new pathways to synthetic problems can be found,
spectral features can be heightened, reactions can be slowed
down, and phase changes investigated, reactive species stabilised
and examined at leisure and a broad range of charge-transfer
species investigated in detail.
In the low temperature spectroscopic field all early research
studies were based on emission studies. The pioneer work on
ethanol glasses by Kautsky (1) was followed by the
phosphoresence studies of aromatics in low temperature glassy
A. I. Barnes et al. (eds.). Matrix Isolation Spectroscopy, 1-11.
Copyright © 1981 by D. Reidel Publishing Company.
