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Published September 15, 1993 | Published
Journal Article Open

Femtosecond real-time probing of reactions. XI. The elementary OClO fragmentation


Femtosecond reaction dynamics of OClO in a supersonic molecular beam are reported. The system is excited to the A 2A2 state with a femtosecond pulse, covering a range of excitation in the symmetric stretch between v1=17 to v1=11 (308–352 nm). A time-delayed femtosecond probe pulse ionizes the OClO, and OClO + is detected. This ion has not been observed in previous experiments because of its ultrafast fragmentation. Transients are reported for the mass of the parent OClO as well as the mass of the ClO. Apparent biexponential decays are observed and related to the fragmentation dynamics: OClO+hnu-->(OClO)[double-dagger]*-->ClO+O -->Cl+O2 . Clusters of OClO with water (OClO)n (H2O)m with n from 1 to 3 and m from 0 to 3 are also observed. The dynamics of the fragmentation reveal the nuclear motions and the electronic coupling between surfaces. The time scale for bond breakage is in the range of 300–500 fs, depending on v1; surface crossing to form new intermediates is a pathway for the two channels of fragmentation: ClO+O (primary) and Cl+O2 (minor). Comparisons with results of ab initio calculations are made.

Additional Information

© 1993 American Institute of Physics. (Received 23 April 1993; accepted 1 June 1993) This work was supported by a grant from the National Science Foundation and from the Air Force Office of Scientific Research. We wish to thank Professor V. Vaida, Professor M. Okumura, and Professor J. Simon for stimulating discussions, and Dr. R. Friedl for his help in the sample preparation.

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