FARADAY DISCUSSIONS OF THE CHEMICAL SOCIETY NO67 1979 Kinetics of State Selected Species THE FARADAY DIVISION CHEMICAL SOCIETY LONDONOrganising Committee Dr. J. P. Simons (Chairman) Dr. A. R. Burgess Prof. R. J. Donovan Mrs. Y. A. Fish Prof. R. Grice Dr. D. M. Hirst Prof. J. C. Robb. Dr. I. W. M. Smith Dr. J. C. Whitehead Dr. D. A. Young ISBN: 0 85186 950 5 ISSN: 0301-7249 0 The Chemical Society and Contributors 1979 Printed in Great Britain by Fletcher & Son Ltd, NorwichA GENERAL DISCUSSION ON Kinetics of State Selected Species 9th, 10th and 11th April, 1979 A GENERAL DISCUSSION on Kinetics of State Selected Species was held at the University of Birmingham on 9th, 10th and 11th April, 1979. The President of the Faraday Division, Professor F. C . Tompkins, F.R.S., was in the chair: about 170 Fellows of the Faraday Division and visitors from overseas attended the meeting.Among the overseas visitors were : Prof. M. Alexander, U.S.A. Dr. J. M. Alvarino, West Germany Prof. F. J. Aoiz, Spain Prof. G. H. Atkinson, U S A . Dr. N. Basco, Canada Dr. R. R. Burke, France Dr. R. J. Buss, U.S.A. Dr. J. E. Butler, U.S.A. Prof. A. Cabello Albala, Spain Prof. F. Castano, Spain Dr. P. N. Clough, West Germany Dr. T . Darko, Sweden Prof. X. De Hemptinne, Belgium Dr. A. Ding, West Germany Mr. K. Eichler, West Germany Dr. H. Figger, West Germany Prof. F. Fleming Crim, U.S.A. Dr. R. Foon, Australia Prof. E. U. Franck, West Germany Prof. K. Freed, U.S.A. Prof. T. F. George, U.S.A. Prof. G. Giacometti, Italy Prof. A. Gonzalez Urena, Spain Prof. P.Gray, West Germany Dr. W. Hack, West Germany Prof. W. L. Hase, U.S.A. Dr. E. F. Hayes, U.S.A. Dr. L. Hellner, France Mr. V. J. Herrero, Spain Mr. H. Heydtmann, West Germany Dr. L. Holmlid, Sweden Prof. P. L. Houston, U.S.A. Prof. W. M. Jackson, U.S.A. Dr. W. Jakubetz, Austria Dr. B. Katz, Israel Prof. K. L. Kompa, West Germany Prof. I. Koyano, Japan Dr. P. J. Kunst, West Germany Mr. L. Lain, Spain Dr. C. Lalo, France Dr. S. Leach, France Dr. H. U. Lee, Wesr Germany Dr. S . R. Leone, U.S.A. Dr. M. R. Levy, U.S.A. Mr D. Lubman, U.S.A. Dr. K. Luther, West Germany Mr. J. P. Martin, France Dr. J. Masanet, France Prof. M. Menzinger, Canada Prof. J. Momigny, Belgium Mr. J. Paris, France Prof. J. C . Polanyi, Canada Prof. E. Poquet, France Dr. K. V. Reddy, U.S.A.Prof. H. Reiss, U.S.A. Dr. C. T. Rettner, U.S.A. Prof. S. A. Rice, U.S.A. Mrs. M. P. Roellig, U.S.A. Dr. G. Rotzoll, West Germany Prof. J. Santarnaria, Spain Prof. G. C . Schatz, U.S.A. Prof. J. L. Schreiber, U.S.A. Prof. D. W. Setser, U.S.A. Prof. P. E. Siska, U.S.A. Dr. J. J. Sloan, Canuda. Prof. F. M. G. Tablas, Spain Dr. K. Tanaka, Japan Dr. G. Venzl, West Germany Dr. J. Wanner, West Germany Dr. K. B. Whaley, U.S.A. Prof. R. N. Zare, U.S.A. Dr. R. Zellner, West GermanyA GENERAL DISCUSSION ON Kinetics of State Selected Species 9th, 10th and 11th April, 1979 A GENERAL DISCUSSION on Kinetics of State Selected Species was held at the University of Birmingham on 9th, 10th and 11th April, 1979. The President of the Faraday Division, Professor F. C . Tompkins, F.R.S., was in the chair: about 170 Fellows of the Faraday Division and visitors from overseas attended the meeting.Among the overseas visitors were : Prof. M. Alexander, U.S.A. Dr. J. M. Alvarino, West Germany Prof. F. J. Aoiz, Spain Prof. G. H. Atkinson, U S A . Dr. N. Basco, Canada Dr. R. R. Burke, France Dr. R. J. Buss, U.S.A. Dr. J. E. Butler, U.S.A. Prof. A. Cabello Albala, Spain Prof. F. Castano, Spain Dr. P. N. Clough, West Germany Dr. T . Darko, Sweden Prof. X. De Hemptinne, Belgium Dr. A. Ding, West Germany Mr. K. Eichler, West Germany Dr. H. Figger, West Germany Prof. F. Fleming Crim, U.S.A. Dr. R. Foon, Australia Prof. E. U. Franck, West Germany Prof. K. Freed, U.S.A. Prof. T. F. George, U.S.A. Prof. G. Giacometti, Italy Prof. A. Gonzalez Urena, Spain Prof.P. Gray, West Germany Dr. W. Hack, West Germany Prof. W. L. Hase, U.S.A. Dr. E. F. Hayes, U.S.A. Dr. L. Hellner, France Mr. V. J. Herrero, Spain Mr. H. Heydtmann, West Germany Dr. L. Holmlid, Sweden Prof. P. L. Houston, U.S.A. Prof. W. M. Jackson, U.S.A. Dr. W. Jakubetz, Austria Dr. B. Katz, Israel Prof. K. L. Kompa, West Germany Prof. I. Koyano, Japan Dr. P. J. Kunst, West Germany Mr. L. Lain, Spain Dr. C. Lalo, France Dr. S. Leach, France Dr. H. U. Lee, Wesr Germany Dr. S . R. Leone, U.S.A. Dr. M. R. Levy, U.S.A. Mr D. Lubman, U.S.A. Dr. K. Luther, West Germany Mr. J. P. Martin, France Dr. J. Masanet, France Prof. M. Menzinger, Canada Prof. J. Momigny, Belgium Mr. J. Paris, France Prof. J. C . Polanyi, Canada Prof. E. Poquet, France Dr. K. V. Reddy, U.S.A.Prof. H. Reiss, U.S.A. Dr. C. T. Rettner, U.S.A. Prof. S. A. Rice, U.S.A. Mrs. M. P. Roellig, U.S.A. Dr. G. Rotzoll, West Germany Prof. J. Santarnaria, Spain Prof. G. C . Schatz, U.S.A. Prof. J. L. Schreiber, U.S.A. Prof. D. W. Setser, U.S.A. Prof. P. E. Siska, U.S.A. Dr. J. J. Sloan, Canuda. Prof. F. M. G. Tablas, Spain Dr. K. Tanaka, Japan Dr. G. Venzl, West Germany Dr. J. Wanner, West Germany Dr. K. B. Whaley, U.S.A. Prof. R. N. Zare, U.S.A. Dr. R. Zellner, West GermanyCONTENTS Page 7 16 27 41 57 66 90 97 110 146 162 173 180 188 204 Polanyi Memorial Lecture by R. N. Zare TRANSLATIONAL EXCITATION Introductory Lecture: Efect of Translational Energy on Reaction Dynamics by R. Grice Reaction of Alkali Metal Atoms with Carbon Tetrachloride: Rainbow-like Couplings of Product Angle and Energy Distribution by S.J. Riley, P. E. Siska and D. R. Herschbach Electronic Excitation in Potentially Reactive Atom-Molecule Collisions by M. A. D. Fluendy, K. P. Lawley, J. McCall, C. Sholeen and D. Sutton Observation of a Condon Reflection Products State Distribution in the Collinear H + C12 Reaction by M. S. Child and K. B. Whaley Distribution of Reaction Products (Theory) : Part I2.--Microscopic Branching in H + XY -+ HX + Y , HY + X (X, Y = Halogens) by J. C. Polanyi, J. L. Schreiber and W. J. Skrlac F + H2 Collisions in the Presence of Intense Laser Radiation: Reactive and Non- Reactive Processes by P. L. DeVries, T. F. George and J.-M. Yuan Vibrational-mode-specijic Energy Consumption: Translational and Vibra- tional State Dependence of the Ba + N20 (vl, u2, u3) -+ BaO* + N2 Reaction by D.J. Wren and M. Menzinger GENERAL DISCUSSION VIBRATIO NAL-ROTATIO NAL EXCITATION Introductory Lecture: Chemical Reaction of Vibrationally Excited Molecules by C. B. Moore and I. W. M. Smith Molecular Beam Studies of Unimolecular Reactions C1, F + C2H3Br by R. J. Buss, M. J. Coggiola and Y. T. Lee Direct Measurement of Photoisomerization Lifetimes for Laser-excited Methylcycloheptatriene Molecules by H. Hippler, K. Luther and J. Troe Wavelength Dependence of Multiphoton Absorption and Dissociation of Hexafluoroace tone by W. FuD, K. L. Kompa and F. M. G. Tablas Reaction Dynamics of State-Selected Unimolecular Reactants: Energy Dependence of the Rate Coeficient for Methyl Isocyanide Isomerization by K.V. Reddy and M. J. Berry Infrared Multiple Phonon Excitation and Dissociation of Single Molecules by M. N. R. Ashfold, G. Hancock and G. Ketley212 221 255 273 286 297 306 316 329 343 363 366 Time-resolved Measurements on the Relaxation of OH(v = 1) by NO, NO2 and O2 by D. H. Jaffer and I. W. M. Smith GENERAL DISCUSSION ELECTRONIC EXCITATION Introductory Lecture: Analogy between Electronically Excited State Atoms and Alkali Metal Atoms by D. W. Setser, T. D. Dreiling, H. C. Brashears, Jr and J. H. Kolts Kinetic Study of Electronically Excited Carbon Atoms C(2'S0) by D. Husain and P. E. Norris Reactions of O(2' D2) and O(23PJ) with Halogenomethanes by M . C. Addison, R. J. Donovan and J. Garraway State-to-State Photochemical Reaction Dynamics in Polyatomic Molecules by K. F. Freed, M. D. Morse and Y. B. Band Pho tofragmen tation Dynamics and Reactive Collisions of Laser-excited Electronic States by S. L. Baughcum, H. Hofmann, S. R. Leone and D. J. Nesbitt Studies of BrCl by Laser-induced Fluorescence: Part 3.-Collision-$ree Dynamics of Quantum Resolved Levels in the Excited B3n (O$) State by M. A. A. Clyne and I. S. McDermid Crossed Beam Studies of Chem ilum inescen t Metastable A tom ic React ions: Excitation Functions and Rotational Polarization in the Reactions of Xe (3P2,0) with Br, and CCl, by C. T. Rettner and J. P. Simons GENERAL DISCUSSION Closing Remarks by S. A. Rice Index of Names