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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 Université des Sciences et Techniques du Languedoc,Montpellier, France, July 17–31,1980 PDF

601 Pages·1981·16.97 MB·English
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Preview 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 Université des Sciences et Techniques du Languedoc,Montpellier, France, July 17–31,1980

Matrix 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 P. O. Box 17, 3300 AA Dordrecht, Holland Sold and distributed in the U.S.A. and Canada by Kluwer Boston Inc., 190 Old Derby Street, Hingham, MA 02043, U.S.A. In all. other countries, sold and distributed by Klu\ver Academic Publishers Group, P.O. Box 322, 3300 AH Dordrecht, Holland D. Reidel Publishing Company is a member of the Kluwer Group All Rights Reserved 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 in any form or by any means, electronic or mechanical, including photocopying, recording or by any informational storage and retrieval system, 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.

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