Femtosecond probing of bimolecular reactions: The collision complex

Femtosecond probing of bimolecular reactions: The collision complex

Progress has been made in probing the femtosecond dynamics of transition states of chemical reactions.* The “half-collision” case of unimolecular reactions has been experimentally investigated for a number of systems and much theoretical work has already been developed.2 For bimolecular reactions, the case of full collision, the zero of time is a problem which makes the femtosecond temporal res...

Femtosecond real-time probing of reactions. VIII. The bimolecular reaction Br+I2

In this paper, we discuss the experimental technique for real-time measurement of the lifetimes of the collision complex of bimolecular reactions. An application to the atom-molecule Br + I, reaction at two collision energies is made. Building on our earlier Communication [J. Chem. Phys. 95, 7763 ( 1991)], we report on the observed transients and lifetimes for the collision complex, the nature ...

Note on the Simple Collision Theory of Bimolecular Reactions.

Femtosecond Dynamics of Unimolecular and Unrestricted Bimolecular Reactions

The results of two time-resolved experiments using femtosecond laser pulses are presented. In the first, molecular photoinduced detachment of I2 from methylene iodide is studied. The progress of the reaction is monitored by selective detection of fluorescence from the iodine product; molecular dynamics are probed by depletion of the fluorescent state. Pump-probe spectroscopy of the halogen moie...

Femtosecond photoassociation: Coherence and implications for control in bimolecular reactions

A theoretical analysis of the recent femtosecond photoassociation spectroscopy ~FPAS! experiment on mercury @U. Marvet and M. Dantus, Chem. Phys. Lett. 245, 393 ~1995!# is presented. It is shown that when a thermal distribution of diatom collision pairs is excited from a free to a bound electronic state on a time scale shorter than molecular vibration, an ensemble of coherent wave packets is pr...