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Published March 1, 1995 | public
Journal Article

Femtosecond Real-Time Probing of Reactions. 17. Centrifugal Effects in Direct Dissociation Reactions

Abstract

The influence of centrifugal repulsion on the real-time photofragmentation dynamics of (quasi)diatomic molecules is investigated. A previously presented classical model (Bersohn, R.; Zewail, A. H. Ber. Bunsenges. Phys. Chem. 1988, 92, 373) for direct dissociation in one (translatory) dimension is invoked to mimic the transient behavior that can be monitored experimentally by femtosecond transition-state spectroscopy. The time-dependent absorption of the probing laser pulse is calculated at transition-state and final product configurations for dissociation with varying amounts of relative rotational angular momentum between separating fragments. In this way, the centrifugal contribution to the potential governing fragmentation is examined in terms of its effect on the characteristic dissociation times for product separation and the lifetimes of transition-state intermediates. Application is made to the photodissociation of ICN via the A continuum, for which it is shown that centrifugal repulsion is not the principal cause of the observed product rotation.

Additional Information

© 1995 American Chemical Society. Received: September 30, 1994; In Final Form: November 29, 1994. Abstract published in Advance ACS Abstracts, February 1, 1995. Financial support of this work by the National Science Foundation and Air Force Office of Scientific Research is gratefully acknowledged. G.R. thanks SERC for the award of a NATO Postdoctoral Fellowship, during the tenure of which this work was carried out.

Additional details

Created:
August 20, 2023
Modified:
October 20, 2023