Springer Series in Chemical Physics 81 Edited by J. P. Toennies
Springer Berlin Heidelberg New York Barcelona Budapest Hong Kong London Milan Paris Santa Clara Singapore Tokyo Springer Series in Chemical Physics Editors: Vitalii I. Goldanskii Fritz P. Schafer J. Peter Toennies Managing Editor: H. K. V. Lotsch
40 High-Resolution Spectroscopy of 52 Multiple-Photon Laser Chemistry Transient Molecules By. R.V. Ambartzumian, C.D. Cantrell, By E. Hirota and A. Puretzky 41 High Resolution Spectral Atlas of 53 Ultrafast Phenomena VII Nitrogen Dioxide 559-597 nm Editors: C. B. Harris, E. P. Ippen, By K. Uehara and H. Sasada G.A. Mourou, and A.H. Zewail 42 Antennas and Reaction Centers of 54 Physics of Ion Impact Phenomena Photosynthetic Bacteria Editor: D. Mathur Structure, Interactions, and Dynamics 55 Ultrafast Phenomena VIII Editor: M.E. Michel-Beyerle Editors: J.-L. Martin, A. Migus, 43 The Atom-Atom Potential Method G. A. Mourou, and A. H. Zewail Applications to Organic Molecular 56 Clusters of Atoms and Molecules Solids Salvation and Chemistry of Free By A.J. Pertsin and A.I. Kitaigorodsky Clusters, and Embedded, Supported and 44 Secondary Ion Mass Spectrometry Compressed Clusters SIMS V Editor: H. Haberland Editors: A. Benninghoven, R. J. Colton, 57 Radiationless Transitions in Poly- D.S. Simons, and H.W. Werner atomic Molecules 45 Thermotropic Liquid Crystals, By E. S. Medvedev and V. I. Osherov Fundamentals 58 Positron Annihilation in Chemistry By G. Vertogen and W.H. de Jeu By O. E. Mogensen 46 Ultrafast Phenomena V 59 Soot Formation in Combustion Editors: G.R. Fleming and Mechanisms and Models A.E. Siegman Editor: H. Bockhorn 47 Complex Chemical Reaction Systems 60 Ultrafast Phenomena IX Mathematical Modelling Editors: P. F. Barbara, W. H. Knox, and Simulation G. A. Mourou, and A. H. Zewail Editors: J. Warnatz and W. Jager 61 Gas Phase Chemical Reaction Systems 48 Ultrafast Phenomena VI Experiments and Models 100 Years Editors: T. Yajima, K. Yoshihara, After Max Bodenstein C. B. Harris, and S. Shionoya Editors: J. Wolfrum, H.-R. Volpp, 49 Vibronic Interactions in Molecules R. Rannacher, and J. Warnatz and Crystals 62 Ultrafast Phenomena X By B. Bersuker and V. Z. Polinger I. Editors: P. F. Barbara, J. G. Fujimoto, 50 Molecular and Laser Spectroscopy W. H. Knox, and W. Zinth By Zu-Geng Wang and Hui-Rong Xia 51 Space-Time Organization in Macro- molecular Fluids Editors: F. Tanaka, M. Doi, and T.Ohta
Volumes 1-39 are listed at the end of the book 1. Wolfrum· H.-R. Volpp R. Rannacher . 1. Warnatz (Eds.) Gas Phase Chemical Reaction Systems Experiments and Models 100 Years After Max Bodenstein
Proceedings of an International Symposion, held at the "Internationales Wissenschaftsforum Heidelberg", Heidelberg, Germany, July 25-28, 1995
With 148 Figures
Springer Professor Dr. J. Wolfrum Professor Dr. J. Warnatz Dr. H.-R. Volpp Interdisziplinlires Zentrum Physikalisch-Chemisches Institut flir WissenschaftIiches Rechnen Universitiit Heidelberg Universitiit Heidelberg 1m Neuenheimer Feld 253 1m Neuenheimer Feld 368 D-69120 Heidelberg, Germany D-69120 Heidelberg, Germany Professor Dr. R. Rannacher Institut flir Angewandte Mathematik Universitat Heidelberg 1m Neuenheimer Feld 293 D-69120 Heidelberg, Germany
Series Editors Professor Dr. Fritz Peter Schafer Max-Planck- Institut flir Biophysikalische Chemie D-37077 Gottingen-Nikolausberg, Germany Professor Vitalii I. Goldanskii Professor Dr. J. Peter Toennies Institute of Chemical Physics Max-Planck- Institut Academy of Sciences flir Stromungsforschung Ulitsa Kossigyna 4 B unsenstrasse 10 Moscow, 117334, Russia D-37073 Gottingen, Germany
Managing Editor: Dr. Helmut K.Y. Lotsch Springer-Verlag, Tiergartenstrasse 17, D-69121 Heidelberg, Germany
Cataloging-in-Publication Data applied for Die Deutsche Bibliothek - CIP-Einheitsaufnahme Gas pbase cbemical raction systems: experiments and models 100 years after Max Bodenstein ; proceedings of an international symposion, held at the Internationales Wissenschaftsforum Heidelberg, Heidelberg, Germany, July 25 - 28, 19951 J. Wolfrum ... (ed.). - Berlin; Heidelberg; New York; Barcelona; Budapest; Hong Kong; London; Mil&..il ; Paris; Santa Clara; Singapore; Tokyo: Springer, 1996 (Springer series in chemical physics ; Vol. 61) ISBN 3-540-61662-4 NE: Wolfrum, Jiirgen [Hrsg.]; Intemationales Wissenschaftsforum
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SPIN: 10545060 54/3144 3 2 10- Printed on acid-free paper Preface
This volume consists of edited papers presented at the International Symposion Gas Phase Chemical Reaction Systems: Experiments and Models 100 Years After Max Bodenslein, held at the Internationales Wissenschaftsforum Heidelberg (IWH) in Heidelberg during July 25-28, 1995. The intention of this symposion was to bring together leading researchers from the fields of reaction dynamics, kinetics, catalysis and reactive flow model• ling to discuss and review the advances in the understanding of chemical kinetics about 100 years after Max Bodenstein's pioneering work on the "hydrogen iodine reaction", which he carried out at the Chemistry Institute of the University of Heidelberg. The idea to focus in his doctoral thesis [1] on this reaction was brought up by his supervisor Victor Meyer (successor of Robert Bunsen at the Chemistry Institute of the University of Heidelberg) and originated from the non• reproducible behaviour found by Bunsen and Roscoe in their early photochemical investigations of the H2/Cl2 system [2] and by van't Hoff [3], and V. Meyer and co-workers [4] in their experiments on the slow combustion of H2/02 mixtures. Whereas earlier work by Hautefeuille [5] and Lemoine [6] on the "behavi• our of hydrogen iodine gas in the heat" and the "photosensitivity of hydrogen iodine" was more of a qualitative character, it was Bodenstein's systematic studies on the thennal [7] and light-induced [8] decomposition of hydrogen iodine, where he combined experimental reaction kinetics studies with mathematical analysis and modelling, that paved the way for modem quantitative treatment of chemical systems of practical interest. Chemical processes occurring in industrial applica• tions, such as in engine combustion or the chemical vapour deposition of diamond, usually consist of a large number of elementary chemical reactions coupled with transport and diffusion phenomena and very often involve heterogeneous reaction steps. Therefore, the development of reliable computational methods for numerical modelling and simulation of such processes necessitates a close and well-coordi• nated interaction across the disciplinary boundaries of mathematics, physics, chemistry, and engineering. In the past, two workshops held here in Heidelberg [9,10] paid tribute to this multidisciplinary challenge, which was also recognized by the foundation of the Interdiszipliniires Zentrumfiir Wissenschaftliches Rechnen (IWR) in 1987 and the subsequent establishment of the Sondeiforschungbereich (SFB) 359: Reaktive Stromungen, Diffusion und Transport at the University of Heidelberg in 1993. It was the encouraging experience and enthusiasm within the research work of the SFB 359 that led to the idea of this symposion, which we hope has achieved its aims, both to remember the historical impact Max Bodenstein had on the develop• ment of chemical kinetics and to allow for intense discussions between scientists who actively work on different aspects of the quantitative investigation and model• ling of chemical reaction systems. Overall about 100 scientists from 10 countries (England, France, Gennany, Hungary, India, Israel, Italy, Sweden, Taiwan, and the U.S.A.) participated, pre• senting and discussing a total of 23 papers and 21 posters and making this sympo• sion a very stimulating one. We hope that this book will transfer a flavour of this stimulating atmosphere to a wider audience. The "Bodenstein family tree" depicted in Fig. I was created - with the enthusiastic help of the participants - during the symposion in order to illustrate
v the scientific connections (rather than strict teacher-student relationships) originat• ing from Max Bodenstein's pioneering work. We by no means intend this tree to be an exhaustive representation of the kinetics community. In addition, for those readers who are interested in more historical details of Max Bodenstein's life we would like to recommend the beautiful article by Erika Cremer [11], in which she describes his scientific life which led him from Heidel• berg (where he received his doctoral degree in 1893), via Berlin, Gottingen, back to Heidelberg (where he published his Habilitation in 1899 [12]), and via Leipzig, Hannover finally again to Berlin, where he became the successor of Nernst in 1923.
This book is divided into six parts (Parts I-VI), reflecting the diversity of the topics discussed during the symposion. Part I is devoted to experimental studies aiming at the elucidation of the microscopic dynamics of elementary reactions by employing laser and molecular beam techniques. The paper that opens this volume was presented by A.H. Zewail and describes the fascinating possibilities femtosecond lasers have offered in chemistry - actually leading to a new branch known as "laser femtochemistry", in which re,!lctive events can nowadays be investigated in real-time (fs) and with atomic (A) resolution. The contributions by H.-R. Volpp and J. Wolfrum, as well as that by F.F. Crim et al. describe experiments in which the influence of selec• tive reagent excitation on the reactivity and product-channels of gas phase elemen• tary reactions is studied by using the laser "pump-and-probe" technique. R.N. Zare, D. W. Chandler and co-workers report on bimolecular reaction product im• aging studies and give a comprehensive description of the reconstruction tech• nique necessary to derive quantum state-resolved three-dimensional scattering in• formation from two-dimensional ion-images of the reaction products. c.B. Moore et al. present results from unimolecular reaction dynamics studies near the disso• ciation threshold, which confirm the fundamental hypothesis of statistical transi• tion state theory. Finally, the contributions by Y.T. Lee et aI., and G.G. Volpi, P. Casavecchia et al. present results from reactive scattering studies of bimolecular three- and four-atom reactions using the cross-molecular-beam method. Part IT is the theoretical counterpart of Part I. The paper by D.G. Truhlar et al. gives an overview of theoretical achievements made in the dynamical treat• ment of the CI + Hz reaction and presents recent results from quantum scattering studies using a new ab initio potential energy surface, which allows for a direct comparison with experimental results from G.G. Volpi, P. Casavecchia et al.. M. Baer and co-workers present a review on their recent quantum mechanical cal• culations for triatomic and tetraatomic systems, which for the H + HzO reaction can be directly compared with the experimental results obtained by H.-R. Volpp and J. Wolfrum. Using the quasiclassical trajectory method, G.c. Schatz et al. studied mode specificity for two different four-atom gas phase reactions which are of importance in combustion chemistry. Employing the same technique T. Raz and R.D. Levine simulated an "exotic" regime of reaction dynamics called "cluster impact-induced chemistry", in which high-barrier processes like the four-center Hz + Iz ~ 2 ill collision mechanism - as suggested by Max Bodenstein for the gas phase reaction - can take place, but in this case inside an impact-heated Xe clus- ter. . Part ill starts with a summary of the current status of the Bodenstein (Hz + Iz) "text book reaction" given by J.B. Anderson, who presented experimental and theoretical results which suggest that at low temperatures the reaction proceeds by a direct bimolecular reaction involving vibration ally excited Iz molecules and a
VI termolecular reaction mechanism, H2 + I + I ~ ill + HI. Both are among the pos• sible reactions already suggested by Max Bodenstein about hundred years ago. In the following paper I. V. Michael reports on recent advances made in the direct measurement of high-temperature bimolecular rate constants, while the paper pres• ented by I. WM. Smith deals with the other extreme: reaction kinetics investiga• tions at ultra-low temperatures. Part IV again is a theoretical one, in which different approaches for the cal• culation of state-specific and thermal rate data are described. The article by A.F. Wagner presents a new approach to describe the influence of hindered rotations on recombination/dissociation kinetics in the framework of transition state theory. In the papers by D. C. Clary and G. Nyman an approximate quantum mechanical method is described and used to calculate thermal rate coefficients for gas phase reactions of interest in atmospheric chemistry which involve poly atomic molecu• les. Finally, different approaches to describe vibrational relaxation of diatoms in thermal collisions are discussed by E.E. Nikitin. Part V includes papers presented in the "heterogeneous reactions"-session, which was opened by G. Ertl, who started by highlighting Max Bodenstein's im• pact on the field of heterogeneous chemical catalysis and then continued by pre• senting some fascinating examples from a rich variety of phenomena, like oscilla• tory and chaotic kinetics, which were observed in the catalytic oxidation of carbon monoxide on Pt(llO) single crystal surfaces. The paper by D.M. Golden et at. de• scribes experimental studies on the chemical interaction between gaseous species with both atmospherically relevant liquid surfaces and soot particles, and empha• sizes the importance of heterogeneous processes in the chemical balance of the stratosphere. The following contribution by I. Warnatz, F. Behrendt and co-work• ers reviews the current status achieved in the numerical simulation of heterogene• ous reaction systems. Hydrocarbon ignition and its chemical kinetic modelling is discussed with reference to a wide range of experimental and practical configura• tions (e.g., internal combustion engines) in the paper presented by C.K. West• brook. Part VI is devoted to the modelling of turbulence, reactive flows and com• plex chemical reaction systems. The paper presented by M. Baum describes the possibilities of direct numerical simulation (DNS) methods with detailed chemical reaction kinetics for the modelling of turbulent combustion. The following paper by Vit.A. Volpert et at. reviews recent experimental and theoretical results on the stability of reaction fronts. In the article by I.A. Miller and P. Glarborg an improved chemical kinetic model for the selective non-catalytic reduction in the "Thermal De-NOx" process is presented. The final contribution of the symposion was given by U. Maas, in which he describes a new approach for the systematic and mathematically correct simplification of chemical kinetics starting from a detailed reaction mechanism. This work points to a promising way of including even complex chemical kinetics into reactive flow simulation codes for practical applications. Although it is almost impossible to cover all aspects of this rapidly develop• ing research field in one book, we feel that the articles in this volume together with the list of references given, reflect the diversity and importance, as well as the ex• citing challenge the investigation of gas phase reaction systems still offers. To thank those who contributed their efforts and energy to make the current symposion a success is a special pleasure for us. Among the first to be mentioned is Mrs. Sylvia Boganski; without her work behind the scenes the organization of the symposion would not have been possible. Our thanks are due to our students Ralph Tadday, Liiko Willms and in particular to Thomas Laurent and to Dr.
VII Rajesh K. Vatsa (on sabbatical leave from BARC Bombay), who were a great help during the whole conference. The very pleasant atmosphere created by Mrs. Dr. Th. Reiter and the staff of the IWH as well as the support from Peter Hoch• stein, Werner Weis and the technical staff of the Physikalisch-Chemisches Institut (PCI) in organizing the poster session also deserves special thanks. Weare very grateful to the "Deutsche Forschungsgemeinschaft" and the SFB 359 at the University of Heidelberg, whose financial support made this sym• posion possible. The partial financial support received from the Alexander von Humboldt-Stiftung via the donation of a 1993 Max-Planck research award is also gratefully acknowledged. Finally, we want to thank Dr. R.A. Brownsword (BC HCM fellow at the PCI) for his help in the technical editing and Dres. H.K. V. Lotsch and W. Skolaut at Springer-Verlag as well as Mrs. Ch. Pendl for their constant advice during the preparation of this volume.
Heidelberg, J. Wolfrum June 1996 H.-R. Volpp R. Rannacher J. Warnatz
References
[1] M. Bodenstein und V. Meyer: Ber. dtsch. chern. Ges. 26, 1146 (1893); M. Bodenstein: ibid., 26, 2603 (1893), II Mitteil. [2] Bunsen, Roscoe: Pogg. Ann. 117,536 (1862). [3] Van't Hoff: Etudes de dynamique chimique, p. 50 ff. (Amsterdam 1884). [4] V. Meyer, Krause, Askenasy: Ann. d. Chern. 264,85 (1891); ibid. 269,85 (1892). [5] Hautefeuille: Compt. rend. 64, 608 (1867). [6] Lemoine: Ann. chim. phys. (5) 12, 145 (1877). [7] M. Bodenstein: Z. phys. Chern. 13, 56 (1894). [8] M. Bodenstein: Z. phys. Chern. 22, 23 (1897). [9] K.H. Ebert, P. Deuflhard, and W. Jager (Eds.), Modelling o/Chemical Reaction Systems, Springer Series in Chern. Phys. Vol. 18 (Berlin, Heidel• berg: Springer-Verlag, 1980). [10] J. Wamatz and W. Jager (Bds.), Complex Chemical Reaction Systems: Mathematical Modelling and Simulation, Springer Series in Chern. Phys. Vol. 47 (Berlin, Heidelberg: Springer-Verlag, 1987). [11] E. Cremer: Max Bodenstein in memoriam, in: Ber. dtsch. chern. Ges. 100, XCV-CXXVI (1967) (incl. list of Max Bodenstein's publications). [12] M. Bodenstein: Gasreaktionen in der chemischen Kinetik, Habilitations• schrift, Universitat Heidelberg (Leipzig, Engelmann, 1899).
VIII x Figure I: "Bodenstein family tree" - Prepared during the conference. Contents
Part I Microscopic Dynamics of Elementary Reactions: Experiment
Femtochemistry and Max Bodenstein's Impact AH. Zewail (With 5 Figures) ...... 3
Laserspectroscopic Studies of Bimolecular Elementary Reaction Dynamics in the Gas Phase H.-R. Volpp and J. Wolfrum (With 7 Figures) ...... 14
Spectators and Participants in Vibrational State Controlled Bimolecular Reactions J.M. Pfeiffer, J.D. Thoemke, R.B. Metz, A Sinha, M.e. Hsiao, E. Woods, and F.F. Crim (With 6 Figures) ...... 32
Reaction Product Imaging: The H + HI Reaction D.W. Chandler, T.N. Kitsopoulos, M.A Buntine, D.P. Baldwin, R.1. McKay, AJ.R. Heck, and R.N. Zare (With 6 Figures) ...... 42
Dynamics at Unimolecular Transition States S.K. Kim, E.R. Lovejoy, and C.B. Moore (With 7 Figures)...... 67
The Reactions of Na2 with 02 H. Hou, K.-T. Lu, V. Sadchenko, AG. Suits, and Y.T. Lee (With 12 Figures) ...... 79
Reaction Dynamics of Three-Atom and Four-Atom Systems M. Alagia, N. Balucani, L. Cartechini, P. Casavecchia, D. Stranges, and G.G. Volpi (With 6 Figures) ...... 96
Part II Microscopic Dynamics of Elementary Reactions: Theory
"Die photochemische Bildung des Chlorwasserstoffs" Dynamics of CI + H2 ~ HCI + H on a New Potential Energy Surface: The Photosynthesis of Hydrogen Chloride Revisited 100 Years After Max Bodenstein T.C. Allison, S.L. Mielke, D.W. Schwenke, G.e. Lynch, M.S. Gordon, and D.G. Truhlar (With 4 Figures)...... 111
Cross Sections and Rate Constants for Triatomic and Tetraatomic Reactions: Three-Dimensional Quantum Mechanical Calculations M. Baer, H. Szichman, E. Rosenman, S. Hochman-Kowal, and A Persky (With 9 Figures)...... 125
XI Mode-Specific Chemistry in the H + HCN and H + N20 Reactions M. ter Horst, K.S. Bradley, and G.C. Schatz (With 4 Figures)...... 144
Dynamics of Chemical Reactions Induced by Cluster Impact T. Raz and R.D. Levine (With 10 Figures)...... 155
Part III Investigations of Thermal Kinetics: Experiment
The Hydrogen-Iodine Reactions: 100 Years Later lB. Anderson (With 2 Figures)...... 167
Recent Advances in the Measurement of High-Temperature Bimolecular Rate Constants J.V. Michael (With 5 Figures)...... 177
Kinetics at Ultra-low Temperatures: Non-Arrhenius Behaviour and Applications to the Chemistry of Interstellar Clouds I.W.M. Smith, B.R. Rowe, and I.R. Sims (With 3 Figures) ...... 190
Part IV State Specific and Thermal Rates: Theory
The Influence of Hindered Rotations on RecombinationlDissociation Kinetics A.F. Wagner, L.B. Harding, S.H. Robertson, and D.M. Wardlaw (With 6 Figures)...... 203
State-to-State Reaction Dynamics of Poly atomic Molecules D.C. Clary (With 2 Figures)...... 216
Effects of OH Rotation on the CH4 + OH ~ CH3 + H20 Reaction G. Nyman (With 2 Figures)...... 223
Pathways of Vibrational Relaxation of Diatoms in the Collisions with Atoms: Manifestation of the Ehrenfest Adiabatic Principle E.E. Nikitin (With 2 Figures)...... 231
Part V Heterogeneous Reactions
Reactions at Surfaces: Bodenstein's Impact and Some Current Aspects G. Ertl (With 5 Figures)...... 245
Heterogeneous Chemistry in the Atmosphere D.M. Golden, C.A. Rogaski, and L.R. Williams (With 4 Figures) ...... 253
Simulation of Heterogeneous Reaction Systems F. Behrendt, O. Deutschmann, B. Ruf, R. Schmidt, and J. Warnatz (With 7 Figures)...... 265
XII Chemical Kinetic Modelling of Hydrocarbon Ignition C.K. Westbrook, W.J. Pitz, H.I. Curran, P. Gaffuri and N.M. Marinov (With 3 Figures)...... 279
Part VI Modelling of Flow, Turbulence and Complex Chemical Reactions
Using Direct Numerical Simulation with Detailed Chemistry to Study Turbulent Combustion M. Baum, M. Hilka, and T.J. Poinsot (With 13 Figures)...... 293
Stability of Reaction Fronts Vit.A. Volpert, VI. A. Volpert, M. Garbey, and J.A. Pojman (With 6 Figures) ...... 309
Modelling the Formation of N20 and N02 in the Thermal De-NOx Process J.A. Miller, and P. Glarborg (With 8 Figures) ...... 318
Simplifying Chemical Kinetics Using Intrinsic Low-Dimensional Manifolds U. Maas (With 4 Figures)...... 334
Index of Contributors...... 343
XIII