Electronic Transitions and the High Pressure Chemistry and Physics of Solids

There is no paucity of books on high pressure. Beginning with P. W. Bridgman's The Physics of High Pressure, books of general interest include the two-volume Physics and Chemistry of High Pressure, edited by R. S. Bradley, and the series, Advances in High

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A. D. Buckingham, University Chemical Laboratory, Cambridge, U.K.

Other titles in the series Advanced Molecular Quantum Mechanics, R. E. Moss Chemical Applications of Molecular Beam Scattering, K. P. Lawley and M. A. D. Fluendy

Electronic Transitions and the High Pressure Chemistry and Physics of Solids

Electronic Transitions and the High Pressure Chemistry and Physics of Solids H. G. DRICKAMER

AND

C. W. FRANK

School of Chemical Sciences and Materials Research Laboratory, University of Illinois, Urbana

CHAPMAN AND HALL· LONDON

First published 1973 by Chapman and Hall Ltd 11 New Fetter Lane, London EC4P 4EE

© 1973 H. G. Drickamer and C. W. Frank Softeover reprint of the hardcover 1st edition 1973 Filmset by Santype Ltd, Salisbury, Wilts. Fletcher & Son Ltd, Norwich, Norfolk

ISBN-13: 978-94-011-6898-4 e-ISBN-13: 978-94-011-6896-0 DOl: 10.1007/978-94-011-6896-0 All rights reserved. No part of this book may be reprinted, or reproduced or utilized in any form or by any electronic, mechanical or other means, now known or hereafter invented, including photocopying and recording, or in any information storage and retrieval system, without permission in writing from the Publisher.

Distributed in the U.S.A. by Halsted Press, a Division of John Wiley & Sons, Inc., New York

Contents

page

ACKNOWLEDGEMENTS

ix

PREFACE

1 Introduction 2 Theories of electronic energy levels

1 In

molecules and

solids 3 Thermal versus optical transitions 4 Phenomenological description of continuous electronic transitions 5 Methods for studying electronic structure at very high pressure 6 Shifts of energy levels with pressure 7 Electronic transitions in metals and insulator-metal transitions 8 Spin changes in iron complexes 9 The reduction of ferric iron 10 Changes of oxidation state and spin state 11 Reactions in aromatic molecules and complexes

vii

viii

6 33 44

60 72 110 126 152 172 185

APPENDIX

210

AUTHOR AND SUBJECT INDEXES

211

Acknowledgements

The authors wish to acknowledge with gratitude permISSIOn to use figures from the following sources: Journal of Chemical Physics, the Physical Review, and Physical Review Letters published by the American Institute of Physics; Proceedings of the National Academy of Sciences published by the Academy; Science published by the American Association for the Advancement of Science; the Journal of Solid State Chemistry published by Academic Press; Journal of Physics and Chemistry of Solids published by Pergamon Press; 'Solid State Physics, Volume 17,' 'The Physics of Solids Under Pressure,' and 'Organic Charge Transfer Complexes' published by Academic Press.

viii

Preface

There is no paucity of books on high pressure. Beginning with P. W. Bridgman's The Physics of High Pressure, books of general interest include the two-volume Physics and Chemistry of High Pressure, edited by R. S. Bradley, and the series, Advances in High Pressure Research, as well as the report on the Lake George Conference in 1960. Solid state physics is well represented by Solids Under Pressure, edited by P