TRANSITION-STATES OF CHARGE-TRANSFER REACTIONS - FEMTOSECOND DYNAMICSAND THE CONCEPT OF HARPOONING IN THE BIMOLECULAR REACTION OF BENZENE WITH IODINE

We describe an approach for real-time Studies of the transition-state dynamics of charge-transfer reactions. An application to the bimolecul ar reaction of benzene with iodine is reported. The measured 750+/-50 fs transient growth of the free I atom product elucidates the nature o f the transition state and the mechanism for the dissociative charge-t ransfer reaction. The mechanism is formulated in relation to the impac t geometry and the dative bonding, which are crucial to condense-phase and surface reactions, and is supported by molecular dynamics. (C) 19 95 American Institute of Physics.