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ADVANCES IN METAL AND SEMICONDUCTOR CLUSTERS Volume3 ,, 1995 SPECTROSCOPY AND STRUCTURE This . Page Intentionally Left Blank ADVANCES IN METAL AND SEMICONDUCTOR CLUSTERS SPECTROSCOPY AND STRUCTURE Editor: MICHAEL A. DUNCAN Department of Chemistry The University of Georgia VOLUME3 9 1995 JA! PRESS INC. Greenwich, Connecticut London, England Copyright 91995 by JAI PRESSINC 55 Old Post Road, No. 2 Greenwich, Connecticut 06836 JAI PRESSLTD. The Courtyard 28 High Street Hampton Hill, Middlesex TWl 2 1PD England All rights reserved. No part of this publication may be reproduced, stored on a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, filming, recording, or otherwise, without prior permission in writing from the publisher. ISBN: 1-55938-788-2 Manufactured in the United States of America CONTENTS LIST OF CONTRIBUTORS vii PREFACE Michael A. Duncan ix METAL ATOM-RARE GAS VANDERWAALS COMPLEXES W. H. Breckenridge, Christophe Jouvet, and Benoit Soep SPECTROSCOPIC STUDIES OF LARGE-AMPLITUDE MOTION IN SMALL CLUSTERS Eric A. Rohlfing 85 STUDY OF SMALL CARBON AND SILICON CLUSTERS USING NEGATIVE ION PHOTODETACHMENT TECHNIQUES Caroline C. Arnold and Daniel M. Neumark 113 CRLAS: A NEW ANALYTICAL TECHNIQUE FOR CLUSTER SCIENCE J. J. Scherer, J. B. Paul, A. O'Keefe, and R. J. Saykally 149 METAL-CARBON CLUSTERS: THE CONSTRUCTION OF CAGES AND CRYSTALS J. S. Pilgrim and M. A. Duncan INDEX 181 223 This . Page Intentionally Left Blank LIST OF CONTRIBUTORS Caroline C. Arnold Department of Chemistry University of California Berkeley, California W. H. Breckenridge Department of Chemistry University of Utah Salt Lake City, Utah Michael A. Duncan Department of Chemistry University of Georgia Athens, Georgia Christophe Jouvet Laboratoire de Photophysique Mol~culaire Universit~ de Paris-Sud Orsay, France Daniel M. Neumark Department of Chemistry University of California Berkeley, California A. O. O'Keefe Deacon Research Palo Alto, California J. B. Paul Department of Chemistry University of California Berkeley, California J. S. Pilgrim Department of Chemistry University of Georgia Athens, Georgia Eric A. Rohlfing Sandia National Laboratories Combustion Research Facility Livermore, California vii viii LISTOF CONTRIBUTORS R. ]. Saykally Department of Chemistry University of California Berkeley, California J. J. 5cherer Department of Chemistry University of California Berkeley, California Benoit 5oep Laboratoire de Photophysique Mol~culaire Universit~ de Paris-Sud Orsay, France PREFACE In Volume 3 of this series, we focus on the complex issues which arise in the determination of the structures of gas phase clusters. Although some cluster systems can now be isolated in bulk (e.g., the fullerenes), cluster science began in the gas phase and there are still more varied examples of clusters in this medium. Breckenridge, Jouvet, and Soep provide a comprehensive review of metal-rare gas complexes, where the details of metal-ligand interactions, electronic structure, and their implications for geometric structure are revealed in detail. Rohlfing looks at small polyatomic systems, where large-amplitude motions are important, making the concept of structure more difficult to define. Arnold and Neumark as well as Scherer, Paul, O'Keefe, and Saykally describe the application of nontraditional spectroscopy techniques and their a