Structurel Reactivity and Thermochemistry of Ions

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1 Structurel Reactivity and Thermochemistry of Ions

2 NATO ASI Series Advanced Science Institutes Series A series presenting the results of activities sponsored by the NA TO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities. The series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division A Life Sciences B Physics C Mathematical and Physical Sciences D Behavioural and Social Sciences E Engineering and Materials Sciences F Computer and Systems Sciences G Ecological Sciences Plenum Publishing Corporation London and New York D. Reidel Publishing Company Dordrecht, Boston, Lancaster and Tokyo Martinus Nijhoff Publishers Dordrecht, Boston and Lancaster Springer-Verlag Berlin, Heidelberg, New York, London, Paris, and Tokyo Series C: Mathematical and Physical Sciences Vol. 193

3 Structu re / Reactivity and Thermochemistry of Ions edited by Pierre Ausloos and Sharon G. Lias Center for Chemical Physics. National Bureau of Standards. Gaithersburg. Maryland. U.S.A. D. Reidel Publishing Company Dordrecht / Boston / Lancaster / Tokyo Published in cooperation with NATO Scientific Affairs Division

4 Proceedings of the NATO Advanced Study Institute on Structure/Reactivity and Thermochemistry of Ions Les Arcs, France June 3~-July 11,1986 Library of Congress Cataloging in Publication Data NATO Advanced Study Institute on Structure/Reactivity and Thermochemistry of Ions (1986 : Les Arcs, France) Structure/reactivity and thermochemistry of ions. (NATO ASI series. Series C, Mathematical and physical sciences; vol. 193) "Published in cooperation with NATO Scientific Affairs Division." Includes index. 1. lons-congresses. 2. Thermochemistry-Congresses. 3. Chemistry, Physical and theoreticai-congresses. I. Ausloos, Pierre J. II. Lias, Sharon G., II. North Atlantic Treaty Organization. SCientific Affairs Division. IV. Title. V. Series: NATO ASI series. Series C, Mathematical and physical sciences; no. 193) QC701.7.N ' ISBN-13: e ISBN-13: DOl: 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 Academic Publishers, 101 Philip Drive, Assinippi Park, Norwell, MA 02061, U.S.A. In all other countries, sold and distributed by Kluwer Academic Publishers Group, P.O. Box 322, 3300 AH Dordrecht, Holland D. Reidel Publishing Company is a member of the Kluwer Academic Publishers Group All Rights Reserved 1987 by D. Reidel Publishing Company, Dordrecht, Holland. Softcover reprint of the hardcover 1st edition 1987 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 information storage and retrieval system, without written permission from the copyright owner.

5 CONTENTS PREFACE vii CAPTURE COLLISION THEORY Douglas P. Ridge 1 COLLISION THEORY: SUMMARY OF THE PANEL DISCUSSION Douglas P. Ridge 15 OPTICAL STUDIES OF PRODUCT STATE DISTRIBUTIONS IN THERMAL ENERGY ION-MOLECULE REACTIONS Veronica M. Bierbaum and Stephen R. Leone CROSSED-MOLECULAR BEAM STUDIES OF CHARGE TRANSFER REACTIONS AT LOW AND INTERMEDIATE ENERGY Jean H. Futrell 2'3 57 PRODUCTION, QUENCHING AND REACTION OF VIBRATIONALLY EXCITED IONS IN COLLISIONS WITH NEUTRALS IN DRIFT TUBES Eldon E. Ferguson KINETIC ENERGY DEPENDENCE OF ION-MOLECULE REACTIONS: FROM TRIATOMICS TO TRANSITION METALS P. B. Armentrout REACTIONS OF TRANSITION METAL IONS WITH CYCLOALKANES AND METAL CARBONYLS Douglas P. Ridge GAS PHASE METAL ION CHEMISTRY: SUMMARY OF THE PANEL DISCUSSION Robert R. Squires DYNAMICS OF DISSOCIATION AND REACTIONS OF CLUSTER IONS A. W. Castleman and R. G. Keesee GROWING MOLECULES WITH ION/MOLECULE REACTIONS.'iethard K. Bohme

6 CONTENTS AB INITIO STUDIES OF INTERSTELLAR MOLECULAR IONS W. P. Kraemer STRUCTURES AND SPECTROSCOPIC PROPERTIES OF SMALL NEGATIVE MOLECULAR IONS - THEORY AND EXPERIMENT P. Botschwina AB INITIO CALCULATIONS ON ORGANIC ION STRUCTURES Nikolaus Heinrich FORMATION OF ANIONS IN THE GAS PHASE Charles H. DePuy and Veronica M. Bierbaum PROTON TRANSFER REACTIONS OF ANIONS Charles H. DePuy and Veronica M. Bierbaum ASSIGNMENT OF ABSOLUTE GAS PHASE BASICITIES OF SMALL MOLECULES T. B. McMahon KINETICS AND EQUILIBRIA OF ELECTRON TRANSFER REACTIONS: A- + B = A + B-. DETERMINATIONS OF ELECTRON AFFINITIES OF A AND B AND STABILITIES OF,ADDUCTS A2- AND (A'B)- Swapan Chowdhury and Paul Kebar1e ION THERMOCHEMISTRY: SUMMARY OF THE PANEL DISCUSSION John E. Bartmess 367 ENTROPY-DRIVEN REACTIONS: SUMMARY OF THE PANEL DISCUSSION Michael Henchman 381 ORGANIC ION/MOLECULE REACTIONS: SUMMARY OF THE PANEL DISCUSSION Nico M. M. Nibbering EXPERIMENTAL AND THEORETICAL STUDIES OF SMALL ORGANIC DICATIONS, MOLECULES WITH HIGHLY REMARKABLE PROPERTIES Wolfram Koch and Helmut Schwarz STRUCTURE AND REACTIVITY OF GASEOUS IONS STUDIED BY A COMBINATION OF MASS SPECTROMETRIC, NUCLEAR DECAY AND RADIOLYTIC TECHNIQUES Fu1vio Cacace INDEX

7 PREFACE This volume presents the proceedings of a 1986 Advanced Study Institute entitled "Structure/Reactivity and Thermochemistry of Ions", held at Les Arcs, France, June 30 to July 11, The format of a NATO Institute is ideally suited to in-depth communications between scientists of diverse backgrounds. Particularly in the field of ion physics and chemistry, where on-going research involves physicists, physical chemists, and organic chemists - who use a variety of experimental and theoretical techniques - it is found that in the relaxed but stimulating atmosphere of a NATO ASI, each professional group provides unique insights, leading to a better definition and solution of problems relating to the properties of gas phase ions. This book presents chapters based on the lectures presented at the Les Arcs ASI. The participants took the initiative to organize a number of specialized workshops - informal discussion groups which considered questions or problem areas of particular interest. The accounts of these sessions, which are also included in this book, make stimulating reading, and include considerable useful information. This Advanced Study Institute is the fourth in a series of NATO-sponsored institutes devoted to the chemistry and physics of ions in the gas phase. The first, in 1974, in Biarritz, France, focussed on "Interactions between Ions and Molecules". This was followed by the 1978 Institute, "Kinetics of Ion/Molecule Reactions" in La Baule, France, and the 1982 ASI on "Ionic Processes in the Gas Phase" in Vimeiro, Portugal, in which emphasis was given to unimolecular processes of ions. A comparison of the Proceedings of the four NATO Advanced Study Institutes presents a clear record of the dramatic experimental and theoretical advances which have been made over the past 12 years in the field of ion physics and chemistry. It has now become possible to elucidate structural, thermochemical, and spectral properties of ions as well as the dynamics of ionic processes, with a degree of detail which was unthought of only a decade ago. vii

8 viii PREFACE Organization of the Les Arcs ASI was initiated by David Dixon, who unfortunately, was unable to attend. We would like to acknowledge his active participation in planning the meeting, as well as the contributions of Keith Jennings, T. B. McMahon, and Rose Marx in planning and running the day-to-day activities at Les Arcs. The Organizing Committee of the 1986 Advanced Study Institute at Les Arcs would like to acknowledge the continuing support and guidance of Dr. Craig Sinclair, Director of the ASI Programme of the Scientific Affairs Division of the North Atlantic Treaty Organization. Pierre Ausloos Sharon G. Lias Gaithersburg, Maryland, U. S. A. October, 1986

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