KOBRA
KOBRA
 Please use this identifier to cite or link to this item: http://nbn-resolving.de/urn:nbn:de:hebis:34-2008102924960

 Title: Femtosecond real-time probing of reactions Other Titles: XI. The elementary OClO fragmentation Authors: Baumert, ThomasHerek, Jennifer L.Zewail, Ahmed H. ???metadata.dc.subject.ddc???: 530 - Physik (Physics) Issue Date: 1993 Citation: In: The Journal of Chemical Physics. - Woodbury, NY : AIP, 99.1993. - S. 4430 - 4440 Abstract: Femtosecond reaction dynamics of OClO in a supersonic molecular beam are reported. The system is excited to the A^2A_2 state with a femtosecond pulse, covering a range of excitation in the symmetric stretch between v_1 = 17 to v_1 = 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+hv \rightarrow (OClO)^{(++)*} \rightarrow ClO+O \rightarrow Cl+O_2. Clusters of OClO with water (OClO)_n (H_2 0)_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 v_1; surface crossing to form new intermediates is a pathway for the two channels of fragmentation: ClO+O (primary) and Cl+O_2 (minor). Comparisons with results of ab initio calculations are made. URI: urn:nbn:de:hebis:34-2008102924960 ISSN: 0021-9606 Appears in Collections: Publikationen

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