FARADAY DISCUSSIONS OF THE CHEMICAL SOCIETY NO. 75 1983 Intramolecular Kinetics THE FAR AD AY DIVISION THE ROYAL SOCIETY OF CHEMISTRY LONDONFARADAY DISCUSSIONS OF THE CHEMICAL SOCIETY NO. 75 1983 Intramolecular Kinetics -WE FARADAY DIVISION 2OYAL SOCIETY OF CHEMISTRY JONA GENERAL DISCUSSION ON Intramolecular Kinetics 18th, 19th and 20th April, 1983 A GENERAL DISCUSSION on Intramolecular Kinetics was held at the University of Warwick on 18th, 19th and 20th April, 1983. The President of the Faraday Division, Professor D. H. Whiffen, FRS, was in the chair: about 150 Fellows of the Faraday Division and visitors from overseas attended the meeting. Among the overseas visitors were : Mr. A. Aspiala, Finland Prof. T. Baer, U.S.A. Dr. J. E. Baggott, U.S.A. Dr. G . D. Billing, Denmark Dr.Biron, France Prof. M. T. Bowers, U.S.A. Dr. W. A. Brand, West Germany Prof. J. Brickmann, West Germany Prof. P. Brumer, Canada Dr. L. Carlsen, Denmark Dr. E. Castellucci, ItaZy Mr. J. H. Catanzarite, U.S.A. Prof. F. F. Crim, U.S.A. Prof. X. De Hemptinne, Belgium Mr. H-R. Dubal, West Germany Dr. G. Dujardin, France Prof. G. E. Ewing, U.S.A. Dr. J. M. Figuera, Spain Prof. A. Foffani, Italy Dr. C. Fotakis, Greece Prof. Y. Haas, Israel Dr. P. Hackett, Canada Dr. E. J. Heller, U.S.A. Prof. J. Hepburn, Canada Prof. R. M. Hochstrasser, U.S.A. Dr. L. Holmlid, Sweden Dr. J. M. Hutson, Canada Dr. J. M. Jasinski, U.S.A. Prof. S . Koda, Japan Dr. P. J. Kuntz, West Germany Dr. S . Leach, France Prof. E. K. C. Lee, U.S.A. Mr. M. Lewerenz, West Germany Prof.C. Lifshitz, Israel Dr. P. Longin, France Prof. J. P. Maier, SwitzerZand Prof. R. A. Marcus, U.S.A. Dr. R. D. McAlpine, Canada Prof. C. B. Moore, U.S.A. Prof. J. T. Muckerman, U.S.A. Dr. R. Naaman, Israel Dr. G. S . Ondrey, West Germany Prof. I. Oref, Israel Prof. D. W. Oxtoby, U.S.A. Prof. C . S . Parmenter, U.S.A. Dr. E. Pollak, Israel Prof. M. Quack, West Germany Prof. R. P. H. Rettschnick, The Netherlands Prof. S . A. Rice, U.S.A. Mr. T. R. Rizzo, U.S.A. Dr. J. Rostas, France Prof. F. S . Rowland, U.S.A. Mr. S . Ruhman, Israel Dr. K. Rynefors, Sweden Prof. J. Santamaria, Spain Dr. J. L. G. Suijker, The Netherlands Prof. J. Troe, West Germany Prof. S . Tsuchiya, Japan Dr. C. A. G. 0. Varma, The Netherlands Dr. G. Vazquez, Mexico Miss K. von Puttkamer, West Germany Mrs. E.Weger, West Germany Dr. B. Whitaker, France Prof. C . Wittig, U.S.A. Prof. I. Yamazaki, Japan Mrs. T. Yamazaki, Japan Prof. R. N. Zare, U.S.A. Prof. A. H. Zewail, U.S.A.Organising Committee Prof. J. P. Simons (Chairman) Dr. M. S. Child Prof. R. J. Donovan Dr. G. Hancock Dr. D. M. Hirst Prof. K. R. Jennings Dr. R. Walsh ISBN: 0-85186-658-1 ISSN : 030 1-7249 Printed in Great Britain by Fletcher & Son Ltd., Norwich.CONTENTS Page 7 23 45 57 77 89 103 117 131 141 155 173 183 197 21 1 223 The Spiers Memorial Lecture; Vibrational Redistribution within Excited Electronic States of Polyatomic Molecules by C. S . Parmenter Intramolecular Relaxation of Excited States of C6F6 + by G. Dujardin and S. Leach Isomerization of Internal-energy-selected Ions by T.Baer, W. A. Brand, T. L. Bunn and J. J. Butler Kinetics of Ion-Molecule Collision Complexes in the Gas Phase. Experiment and Theory by M. T. Bowers, M. F. Jarrold, W. Wagner-Redeker, P. R. Kemper and L. M. Bass Intramolecular Decay of Some Open-shell Polyatomic Cations by J. P. Maier, M. Ochsner and F. Thommen GENERAL DISCUSSION On the Theory of Intramolecular Energy Transfer by R. A. Marcus Pulsed Laser Preparation and Quantum Superposition State Evolution in Regular and Irregular Systems by R. D. Taylor and P. Brumer A Quantum-mechanical Internal-collision Model for State-selected Uni- molecular Decomposition by B. K. Holmer and M. S. Child The Correspondence Principle and Intramolecular Dynamics by E. J. Heller GENERAL DISCUSSION Intramolecular Dephasing.Picosecond Evolution of Wavepacket States in a Molecule with Intermediate-case level Structure by D. D. Smith, S. A. Rice and W. Struve Energy Conversion in Van der Waals Complexes of s-Tetrazine and Argon by J. J. F. Ramaekers, H. K. van Dijk, J. Langelaar and R. P. H. Rettschnick Time-dependent Processes in Polyatomic Molecules During and After Intense Infrared Irradiation by K. von Puttkamer, H-R. Dubal and M. Quack Energy Distributions in the CN(X 'C') Fragment from the Infrared Multiple- photon Dissociation of CF,CN. A Comparison between Experimental Results and the Predictions of Statistical Theories by J. R. Beresford, G. Hancock, A. J. MacRobert, J. Catanzarite, G. Radhakrishnan, H. Reisler and C. Wittig Product Energy Partitioning in the Decomposition of State-selectively Excited HOON and HOOD by T.R. Rizzo, C. C. Hayden and F. F. Crim239 251 289 30 1 315 33 1 341 365 377 387 395 407 424 428 430 Low-power Infrared Laser Photolysis of Tetramethyldioxetan by S. Ruhman, 0. Anner and Y. Haas GENERAL DISCUSSION Unirnolecular Reactions Induced by Vibrational Overtone Excitation by J. M. Jasinski, J. K. Frisoli and C. B. Moore Unimolecular Decomposition of t-Butylhydroperoxide by Direct Excitation of the 6-0 0-H Stretching Overtone- by M-C. Chuang, J. E. Baggott, D. W. Chandler, W. E. Farneth and R. N. Zare Picosecond-jet Spectroscopy and Photochemistry. Energy Redistribution and its Impact on Coherence, Isomerization, Dissociation and Solvation by A. H. Zewail Energy Redistribution in Large Molecules. Relaxation in the Gas Phase with Picosecond Gating by R. Moore, F. E. Doany, E. J. Heilweil and R. M. Hochstrasser GENERAL DISCUSSION Direct Study of Intramolecular Rotation-dependent Intramolecular Processes of S02(A ' A z ) in a Supersonic Jet by H. Watanabe, S. Tsuchiya and S. Koda Role of Rotation- Vibration Interaction in Vibrational Relaxation. Energy Redistribution in Excited Singlet Formaldehyde by N. L. Garland and E. K. C. Lee Sub- Doppler Spectroscopy of Benzene in the " Channel-three " Region by E. Riedle, H. J. Neusser and E. W. Schlag Intramolecular Electronic Relaxation and Photoisornerization Processes in the Isolated Azabenzene Molecules Pyridine, Pyrazine and Pyrimidine by I. Yamazaki, T. Murao, T. Yamanaka and K. Yoshihara GENERAL DISCUSSION ADDITIONAL REMARKS LIST OF POSTERS INDEX OF NAMES