Advances in CHEMICAL PHYSICS Chemical Reactions and Their Control on the Femtosecond Time Scale XXth Solvay Conference on Chemistry

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Advances in CHEMICAL PHYSICS Chemical Reactions and Their Control on the Femtosecond Time Scale XXth Solvay Conference on Chemistry Edited by PIERRE GASPARD Center for Nonlinear Phenomena and Complex Systems Universite Libre de Bruxelles Brüssels, Belgium and IRENE BURGHARDT Institut für Physikalische und Theoretische Chemie der Universität Bonn Bonn, Germany Series Editors I. PRIGOGINE STUART A. RICE Center for Studies in Statistical Mechanics and Complex Systems The University of Texas Austin, Texas and International Solvay Institutes Universite Libre de Bruxelles Brüssels, Belgium Department of Chemistry and The James Franck Institute The University of Chicago Chicago, Illinois VOLUME 101 AN INTERSCIENCE^ PUBLICATION JOHN WILEY & SONS, INC. NEW YORK. CHICHESTER. WEINHEIM BRISBANE. SINGAPORE. TORONTO

CONTENTS OPENING REMARKS xxxi J. Solvay FEMTOCHEMISTRY: FROM ISOLATED MOLECULES TO CLUSTERS FEMTOCHEMISTRY: CHEMICAL REACTION DYNAMICS AND THEIR CONTROL 3 A. H. Zewail Discussion on the Report by A. H. Zewail COHERENT CONTROL WITH FEMTOSECOND LASER PULSES 47 T. Baumert, J. Helbing, and G. Gerber Discussion on the Report by G. Gerber GENERAL DISCUSSION ON FEMTOCHEMISTRY: FROM ISOLATED MOLECULES TO CLUSTERS 83 FEMTOCHEMISTRY: FROM CLUSTERS TO SOLUTIONS SIZE-DEPENDENT ULTRAFAST RELAXATION PHENOMENA IN METAL CLUSTERS 101 R. S. Berry, V. Bonacic-Koutecky, J. Gaus, Th. Leisner, H. Ruppe, S. Rutz, E. Schreiber, St. Vajda, S. Wolf, L. Wöste, J. Manz, B. Reischl-Lenz, and R. de Vivie-Riedle Discussion on the Report by L. Wöste FEMTOSECOND CHEMICAL DYNAMICS IN CONDENSED PHASES 141 G. R. Fleming, T. Joo, and M. Cho Discussion on the Report by G. R. Fleming FEMTOSECOND LASER CONTROL OF ELECTRON BEAMS FOR ULTRAFAST DIFFRACTION 185 V. S. Letokhov Discussion on the Communication by V. S. Letokhov xxv

XXVI CONTENTS GENERAL DISCUSSION ON FEMTOCHEMISTRY: FROM CLUSTERS TO SOLUTIONS 193 LASER CONTROL OF CHEMICAL REACTIONS PERSPECTIVES ON THE CONTROL OF QUANTUM MANY-BODY DYNAMICS: APPLICATION TO CHEMICAL REACTIONS 213 S. A. Rice Discussion on the Report by S. A. Rice EXPERIMENTAL OBSERVATION OF LASER CONTROL: ELECTRONIC BRANCHING IN THE PHOTODISSOCIATION OF Na 2 285 A. Shnitman, I. Sofer, I. Golub, A. Yogev, M. Shapiro, Z. Chen, and P. Brumer Discussion on the Communication by M. Shapiro COHERENT CONTROL OF BIMOLECULAR SCATTERING 295 P. Brumer and M. Shapiro LASER HEATING, COOLING, AND TRANSPARENCY OF INTERNAL DEGREES OF FREEDOM OF MOLECULES 301 D. J. Tannor, R. Kosloff, and A. Bartana Discussion on the Communication by D. J. Tannor RAMIFICATIONS OF FEEDBACK FOR CONTROL OF QUANTUM DYNAMICS 315 H. Rabitz Discussion on the Communication by H. Rabitz THEORY OF LASER CONTROL OF VIBRATIONAL TRANSITIONS AND CHEMICAL REACTIONS BY ULTRASHORT INFRARED LASER PULSES 327 M. V. Korolkov, J. Manz, and G. K. Paramonov Discussion on the Communication by J. Manz TIME-FREQUENCY AND COORDINATE-MOMENTUM WIGNER WAVEPACKETS IN NONLINEAR SPECTROSCOPY 345 S. Mukamel, C. Ciordas-Ciurdariu, and V. Khidekel GENERAL DISCUSSION ON LASER CONTROL OF CHEMICAL REACTIONS 373

CONTENTS XXV11 INTRAMOLECULAR DYNAMICS SOLVENT DYNAMICS AND RRKM THEORY OF CLUSTERS 391 R. A. Marcus Discussion on the Report by R. A. Marcus HIGH-RESOLUTION SPECTROSCOPY AND INTRAMOLECULAR DYNAMICS 409 H. J. Neusser and R. Neuhauser Discussion on the Report by H. J. Neusser GENERAL DISCUSSION ON INTRAMOLECULAR DYNAMICS 449 REGULÄR AND IRREGULÄR FEATURES IN UNIMOLECULAR SPECTRA AND DYNAMICS INTRAMOLECULAR DYNAMICS IN THE FREQUENCY DOMAIN 463 R. W. Field, J. P O'Brien, M. P Jacobson, S. A. B. Solina, W. F. Polik, and H. Ishikawa EMERGENCE OF CLASSICAL PERIODIC ORBITS AND CHAOS IN INTRAMOLECULAR AND DISSOCIATION DYNAMICS 491 P. Gaspard and I. Burghardt GENERAL DISCUSSION ON REGULÄR AND IRREGULÄR FEATURES IN UNIMOLECULAR SPECTRA AND DYNAMICS 583 MOLECULAR RYDBERG STATES AND ZEKE SPECTROSCOPY ZEKE SPECTROSCOPY 607 E. W. Schlag Discussion on the Report by E. W. Schlag SEPARATION OF TIME SCALES IN THE DYNAMICS OF HIGH MOLECULAR RYDBERG STATES 625 R. D. Levine GENERAL DISCUSSION ON MOLECULAR RYDBERG STATES AND ZEKE SPECTROSCOPY: PART I 647

XXV111 CONTENTS FROM RYDBERG STATE DYNAMICS TO ION-MOLECULE REACTIONS USING ZEKE SPECTROSCOPY 667 T. P. Sofiley, S. R. Mackenzie, F. Merkt, and D. Rolland Discussion on the Report by T. P. Sofiley QUANTUM DEFECT THEORY OF THE DYNAMICS OF MOLECULAR RYDBERG STATES 701 Ch. Jungen Discussion on the Report by Ch. Jungen SUBPICOSECOND STUDY OF BUBBLE FORMATION UPON RYDBERG STATE EXCITATION IN CONDENSED RARE GASES 711 M.-T. Portella-Oberli, C. Jeannin, and M. Chergui Discussion on the Communication by M. Chergui GENERAL DISCUSSION ON MOLECULAR RYDBERG STATES AND ZEKE SPECTROSCOPY: PART II 719 TRANSITION-STATE SPECTROSCOPY AND PHOTODISSOCIATION PHOTODISSOCIATION SPECTROSCOPY AND DYNAMICS OF THE VINOXY (CH 2 CHO) RADICAL 729 D. L. Osborn, H. Choi, and D. M. Neumark Discussion on the Report by D. M. Neumark RESONANCES IN UNIMOLECULAR DISSOCIATION: FROM MODE-SPECIFIC TO STATISTICAL BEHAVIOR 745 R. Schinke, H.-M. Keller, H. Flöthmann, M. Stumpf, C. Beck, D. H. Mordaunt, and A. J. Dobbyn Discussion on the Report by R. Schinke PHOTODISSOCIATING SMALL POLYATOMIC MOLECULES IN THE VUV REGION: RESONANCES IN THE 1 E + - 1 E + BAND OF OCS 789 K. Yamanouchi, K. Ohde, and A. Hishikawa Discussion on the Communication by K. Yamanouchi PHASE AND AMPLITUDE IMAGING OF EVOLVING WAVEPACKETS BY SPECTROSCOPIC MEANS 799 M. Shapiro Discussion on the Communication by M. Shapiro

CONTENTS XXIX GENERAL DISCUSSION ON TRANSITION-STATE SPECTROSCOPY AND PHOTODISSOCIATION 809 REACTION RATE THEORIES RECENT ADVANCES IN STATISTICAL ADIABATIC CHANNEL CALCULATIONS OF STATE-SPECIFIC DISSOCIATION DYNAMICS 819 J. Troe Discussion on the Report by J. Troe QUANTUM AND SEMICLASSICAL THEORIES OF CHEMICAL REACTION RATES 853 W. H. Miller Discussion on the Report by W. H. Miller FEMTOSPECTROCHEMISTRY: NOVEL POSSIBILITIES WITH THREE-DIMENSIONAL (SPACE-TIME) RESOLUTION 873 V. S. Letokhov Discussion on the Communication by V. S. Letokhov ACADEMIC SESSION AT THE CASTLE OF LAEKEN: PRESENTATION TO KING ALBERT II 889 MODERN PHOTOCHEMISTRY 889 S. A. Rice FEMTOCHEMISTRY 892 A. H. Zewail CONCLUDING REMARKS 893 S. A. Rice and V. S. Letokhov AUTHOR INDEX 899 SUBJECT INDEX 927