Energetics of Stable Molecules and Reactive Intermediates PDF
Preview Energetics of Stable Molecules and Reactive Intermediates
Energetics of Stable Molecules and Reactive Intermediates NATO Science Series A Series presenting the results of activities sponsored by the NA TO Science Committee. The Series is published by lOS Press and Kluwer Academic Publishers, in conjunction with the NA TO Scientific Affairs Division. A. Life Sciences lOS Press B. Physics Kluwer Academic Publishers C. Mathematical and Physical Sciences Kluwer Academic Publishers D. Behavioural and Social Sciences Kluwer Academic Publishers E. Applied SCiences Kluwer Academic Publishers F. Computer and Systems Sciences lOS Press 1. Disarmament Technologies Kluwer Academic Publishers 2. Environmental Security Kluwer Academic Publishers 3. High Technology Kluwer Academic Publishers 4. Science and Technology Policy lOS Press 5. Computer Networking lOS Press NATO-PCO-DATA BASE The NATO Science Series continues the series of books published formerly in the NATO ASI Series. An electronic index to the NATO ASI Series provides full bibliographical references (with keywords and/or abstracts) to more than 50000 contributions from international scientists published in all sections of the NATO ASI Series. Access to the NATO-PCO-DATA BASE is possible via CD-ROM "NATO-PCO-DATA BASE" with user-friendly retrieval software in English, French and German (© WTV GmbH and DATAWARE Technologies Inc. 1989). The CD-ROM of the NATO ASI Series can be ordered from: PCO, Overijse, Belgium. Series C: Mathematical and Physical Sciences - Vol. 535 Energetics of Stable Moleeules and Reactive Intermediates edited by M.E. Minas da Piedade Centro de Qufmica Estrutural, Complexo Interdisciplinar, Instituto Superior Tecnico, Lisboa, Portugal Springer Science+Business Media, B.V. Proceedings of the NATO Advanced Study Institute on Energetics of Stable Moleeules and Reactive Intermediates Castelo Branco, Portugal 14--24 July 1998 A C.I.P. Catalogue record for this book is available from the Library of Congress ISBN 978-0-7923-5741-4 ISBN 978-94-011-4671-5 (eBook) DOI 10.1007/978-94-011-4671-5 Printed on acid-free paper All Rights Reserved © 1999 Springer Science+Business Media Dordrecht Originally published by Kluwer Academic Publishers in 1999 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 photo copying, recording or by any information storage and retrieval system, without written permission trom the copyright owner. CONTENTS Preface VlI 1. EXPERIMENTAL METHODS TO DERIVE BOND ENERGY DATA. A SCHEMATIC OVERVIEW J.A. Martinho Simoes· and MA. V. Ribeiro da Silva 2. OXYGEN BOMB COMBUSTION CALORIMETRY: PRINCIPLES AND APPLICATIONS TO ORGANIC AND ORGANOMETALLIC 29 COMPOUNDS Manuel E. Minas da Piedade 3. THE NUTS AND BOLTS AND RESULTS OF FLUORINE BOMB CALORIMETRY 55 P.A. G. O'Hare 4. TITRATION CALORIMETRY FOR THE DETERMINATION OF BASICITIES OF TRANSITION METAL COMPLEXES 77 Robert J. Angelici 5. PHOTO CALORIMETRY. METHODS AND APPLICATIONS 105 Clementina Teixeira 6. PHOTOACOUSTIC CALORIMETRY; THE DETERMINATION OF BOND DISSOCIATION ENTHALPIES IN SOLUTION AND IN THE GAS PHASE 137 LucasJ. J. Laarhoven, Peter Mulder*, and Danial D. M Wayner 7. ENERGETICS OF TRANSITION METAL-X BONDING PROBED BY ELECTROCHEMICAL TECHNIQUES 153 Mats Tilset 8. A PROTOCOL FOR DERIVING VA LVES FOR ~fu.Hm(298.15 K) AND ~vapffm (298.15 K). APPLICATIONS IN OBT AINING ~suJfm(298.15 K) 177 James Chickos*, Gary Nichols, Joe Wilson, Jennifer Orf, Paul Webb, and Jin Wang 9. MEASUREMENTS OF ENTHALPIES OF SUBLIMATION: THE IMPORTANCE OF CORRELATING THERMODYNAMIC DATA OBT AINED FROM INDIRECT METHODS 203 Manuel JOGO S. Monte Vi 10. APPLICATIONS OF TRANSIENT INFRARED SPECTROSCOPY TO COORDINATIVEL Y UNSATURATED METAL CARBONYLS 215 Eric Weitz 11. ENERGETICS AND STRUCTURES OF GAS PHASE IONS: MACROMOLECULES, CLUSTERS AND LIGATED TRANSITION METALS 235 Michael T. Bowers*, Paul R. Kemper, Petra van Koppen, Thomas Wyttenbach, Catherine 1. Carpenter, Patrick Weis, and Jennifer Gidden 12. HIGH PRESURE MASS SPECTROMETRY. INSTRUMENT AT ION, TECHNIQUES AND APPLICATIONS 259 T.B. McMahon 13. FT ICR. BASIC PRINCIPLES AND SOME REPRESENT AT IVE APPLICATIONS 281 Jose Luis, M Abboud*, and Rafael Notario 14. THE ROLE OF ION DISSOCIATION DYNAMICS IN THE STUDY OF ION AND NEUTRAL THERMOCHEMISTRY 303 Tomas Baer*, Rick Lafleur, and Oleg Mazyar 15. SHOCK TUBE STUDIES ON THE STABILITY OF POLYATOMIC MOLECULES AND THE DETERMINATION OF BOND ENERGIES 323 Wing Tsang 16. EXTRACTING THERMOCHEMICAL INFORMATION FROM AB INITIO DATA 353 Karl K. lrikura 17. AB INITIO THERMOCHEMISTRY BEYOND CHEMICAL ACCURACY FOR FIRST-AND SECOND-ROW COMPOUNDS 373 Jan M L. Martin 18. HEATS OF FORMATION BY DENSITY FUNCTIONAL THEORY CALCULATIONS 417 NL. Allinger List of Participants 431 Subject Index 439 PREFACE The study of molecular bonding energetics and reactivity requires a reliable and as vast as possible databank on thermodynamic and kinetic values, such as standard enthalpies of formation, bond dissociation enthalpies, ionization energies, energies of activation, etc .. Throughout the last two decades, major advances in classical experimental techniques (e. g. the emergence of micro combustion calorimetry) and the development of a considerable number of new methods (e. g. photoacoustic calorimetry and several mass spectrometry teclmiques), allowed studies of many stable molecules and reactive intermediates which, until then, were beyond reach. These studies are currently having a major impact on organic, inorganic, and organometallic chemistry, and also on related areas such as catalysis, biochemistry and enviroumental chemistry. There is, however, a large difference between the sizes of the experimental databanks and tlle number of known molecules, and this gap increases everyday. Fortunately, the experimental progresses referred to above have been paralleled by the development of several empirical estimation schemes and metllods based on quantum chemistry calculations. Due to the availability of fast and powerful computers, a wealth of tlleoretical results are currently being derived, which, in some cases, have reached tile limits of the experimental accuracy. To review the state of the art and show the interplay of some of the most important experimental and theoretical methods currently used to probe the bonding energetics and reactivity of a large diversity of chemical species was the major purpose of the NATO Advanced Study Institute Energetics of Stable Molecules and Reactive Intermediates, held in Castelo Branco, Portugal, in July 1998. The school consisted of a number of tutorials where the methods and representative applications were presented and discussed with enough detail to foster interaction Witll the audience. Practical sessions involving simple computational chemistry calculations, poster sessions, and a panel session on 'Thennochemistry Databases and the Need for New Data' were also included in tlle progranune. This book contains the main lectures presented at tile AS!. It is hoped that it will be a valuable introduction to tile study of molecular energetics and also a reference for autllOrs currently involved in tllis field. The first chapter is a general and very concise overview of the experimental methods used to determine bond energies. The next six chapters are dedicated to methods used to study condensed phase species. Chapters 8 and 9 are devoted to the detennination and estimation of phase transition enthalpies, which are frequently needed to link gas phase and condensed phase data. Methods used to study gas phase species are addressed in chapters 10 to 15. The three final chapters cover theoretical methods which are likely to become of increasing importance in deriving tllermochemical quantities. vii Vlll The kind support and advice from tile NATO Scientific Affairs Division (ASI Programme Director Dr. Luis Veiga da Cunha) is gratefully acknowledged. I also would like to express my gratitude to tlle following organizations for support of tile AS!: Camara Municipal de Castelo Branco (Portugal), NERCAB - Associa~ao Empresarial da Regiao de Castelo Branco (Portugal), Escola Superior de Tecnologia de Castelo Branco (Portugal), Funda~ao para a Ciencia e a Tecnologia (Portugal), Luso-American Foundation for tile Development, Instituto Superior Tecnico (Portugal), Portugal Telecom, S. A., Telepac - Sevi~os de Telecomunica~oes S. A. (Portugal), MSFT, Lda. (Subsidiary of Microsoft Corporation), Gaussian, Inc., Tripos, Inc., CambridgeSoft Corp., National Institute of Standards and Technology (U.S.A.), National Science Foundation (U.S.A.), Caixa Geral de Depositos (Portugal), Canon Copicanola, and Expo 98. Very special tIlanks to Dr. Karl K. Irikura, Prof. 1. A. Martinho Simoes and Prof. Mats Tilset from tlle Scientific Organising Committee of the ASI, and particularly to Drs. Herminio Diogo and Joao Paulo Leal, from tile Local Organising Committee. M. E. Minas da Piedade January 1999. EXPERIMENTAL METHODS TO DERIVE BOND ENERGY DATA. A SCHEMATIC OVERVIEW J. A. MARTINHO SIMOES Departamento de Quimica e Bioquimica Faculdade de Ciencias Universidade de Lisboa 1749-016 Lisboa, Portugal M. A V. RIBEIRO DA SIL VA Departamento de Quimica Faculdade de Ciencias Universidade do Porto Rua do Campo Alegre, 687 4169-007 Porto, Portugal ABSTRACT. This paper is a brief account of the most important experimental methods used to investigate the thermodynamic stability of molecules and chemical bonds. 1. Introduction Molecular Energetics (or Molecular Thermochemistry) is concerned with the study of the thermodynamic stability of molecules and chemical bonds. This knowledge is useful in several areas of science and technology, but its major importance comes from the contribution it provides to the understanding of what is, perhaps, the most fundamental issue in Chemistry: the energetics-structure-reactivity relationships. What tools are available to investigate the energetics of molecules and bonds? How reliable are they? And what is the application range of each of them? These questions have been partially answered throughout this book, which contains the description and application examples of a fair number of experimental and computational thermochemistry methodologies. However, the list is far from comprehensive -there are many other laboratory techniques that have been and are being used to investigate the stability of chemical species. The present chapter aims to reduce the gap by providing a ME MilUlS da Piedade (ed.), Energetics of Stable Molecules and Reactive Intermediates. 1-28. © 1999 Kluwer Academic Publishers. 2 very concise description and assessment of many of those methods. It must therefore be regarded as a starting point for the non-expert reader. We will not attempt to describe experimental set-ups. Instead, we will concentrate on a few topics that are relevant to consider when using or discussing data obtained through each method. However, it is stressed that the correct relationships between thermodynamic functions and the quantities measured with some of the newer techniques are often not straightforward and would deserve a careful and more detailed analysis. We hope that this task will be completed in the near future [1]. The methods covered in Section 2, by alphabetical order, are summarized in Table 1. Table 1 Experimental methods addressed in this paper Condensed phase methods Gas phase methods Combustion Calorimetry (CC) Birge-Sponer Extrapolation (BS) Differential Scanning Calorimetry (DSC) Electron Impact Mass Spectrometry (ElMS) Electrochemical Measurements (EChem) Electron Photodetachment Spectroscopy (EPDS) Equilibrium in Solution (ES) Equilibrium in the Gas Phase (EG) Kinetics in Solution (KS) Flowing Afterglow -Selected Ion-Flow Tube (FA-SIFT) Photoacoustic Calorimetry (PAC) Guided Ion Beam Mass Spectrometry (GIBMS) Photocalorimetry (PC) High Pressure Mass Spectrometry (HPMS) Reaction-Solution Calorimetry (RSC) Ion Cyclotron Resonance Mass Spectrometry (ICR) Titration Calorimetry (TC) Kinetic Energy Release Distributions (KERD) Kinetics in the Gas Phase (KG) Knudsen Cell-Mass Spectrometry (KC-MS) Laser-Powered Homogeneous Pyrolysis (LPHP) Mass Spectrometry -Kinetic Method (MS-K) Photoelectron Spectroscopy (PES) Photoionization Mass Spectrometry (PlMS) Pulsed High Pressure Mass Spectrometry (PHPMS) Single-Pulse Shock Tubes (SPST) Very Low Pressure Pyrolysis (VLPP) 2. Experimental Methods 2.1 BIRGE-SPONER EXTRAPOLATION (BS) [2,3] Measured quantities Spacing of vibrational energy levels. Primary quantities derived Bond dissociation enthalpies at 0 K. Secondary quantities derived Bond dissociation enthalpies at 298.15 K.
The list of books you might like
