ADVANCES IN GAS PHASE ION CHEMISTRY Volume 2 1996 This Page Intentionally Left Blank ADVANCES IN GAS PHASE ION CHEMISTRY Editors" NIGEL G. ADAMS LUCIA M. BABCOCK Department of Chemistry The University of Georgia VOLUME 2 9 1996 Greenwich, Connecticut @ JAI PRESS INC. London, England Copyright 91996 by JAI PRESSINC 55 Old Post Road, No. 2 Greenwich, Connecticut 06836 JAI PRESSLTD. The Courtyard 28 High Street Hampton Hill, Middlesex TW12 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: 1-55938-703-3 Manufactured in the United States of America CONTENTS LIST OF CONTRIBUTORS PREFACE Nigel G. Adams and Lucia M. Babcock ~ VII ix EFFECT OF MOLECULAR ORIENTATION ON ELECTRON TRANSFER AND ELECTRON IMPACT IONIZATION Philip R. Brooks and Peter W. Harland EXPERIMENTAL APPROACHES TO THE UNIMOLECULAR DISSOCIATION OF GASEOUS CLUSTER IONS Terrance B. McMahon NEW APPROACHES TO ION THERMOCHEMlSTRY VIA DISSOCIATION AND ASSOCIATION Robert C. Dunbar 41 87 ALKYL CATION-DIHYDROGEN COMPLEXES; SILONIUM AND GERMONIUM CATIONS: THEORETICAL CONSIDERATIONS Peter R. Schreiner, Henry F. Schaefer III, and Paul v.
[email protected] SYMMETRY-INDUCED KINETIC ISOTOPE EFFECTS IN ION-MOLECULE REACTIONS Gregory I. Gellene 125 161 vi CONTENTS ION-MOLECULE CHEMISTRY: THE ROLES OF INTRINSIC STRUCTURE, SOLVATION, AND COUNTERIONS John E. Bartmess 193 GAS PHASE ION CHEMISTRY UNDER CONDITIONS OF VERY HIGH PRESSURE W. Berk Knighton and Eric P. Grimsrud 219 INDEX 259 LIST OF CONTRIBUTORS John E. Bartmess Department of Chemistry University of Tennessee Knoxville, Tennessee Philip R. Brooks Department of Chemistry Rice University Houston, Texas Robert C. Dunbar Department of Chemistry Case Western Reserve University Cleveland, Ohio Gregory I. Gellene Department of Chemistry and Biochemistry Texas Tech University Lubbock, Texas Eric P. Grimsrud Department of Chemistry Montana State University Bozeman, Montana Peter W. Harland Department of Chemistry University of Canterbury Christchurch, New Zealand W. Berk Knighton Department of Chemistry Montana State University Bozeman, Montana Terrance B. McMahon Department of Chemistry University of Waterloo Waterloo, Ontario, Canada vii viii LIST OF CONTRIBUTORS Henry F. Schaefer Iii Center for Computational Quantum Chemistry University of Georgia Athens, Georgia Paul v. Ragu~ Schleyer Center for Computational Quantum Chemistry University of Georgia Athens, Georgia Peter R. Schreiner Center for Computational Quantum Chemistry University of Georgia Athens, Georgia PREFACE Gas phase ion chemistry is a broad field with many applications which encompasses various branches of chemistry and physics. It is continually developing, with new approaches to obtaining kinetic (Knighton and Grimsrud) and thermochemical (McMahon; Dunbar) data under a wide variety of experimental conditions and with new insights into the mechanisms of ion--molecule reactions (Gellene; Bartmess) and the parameters which control them. It is becoming increasingly obvious that progres