Aufsatz![](/themes/Mirage2/images/Open_Access_logo_PLoS_transparent.svg)
Femtosecond real-time probing of reactions
(XI. The elementary OClO fragmentation)
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.
Citation
In: The Journal of Chemical Physics. - Woodbury, NY : AIP, 99.1993. - S. 4430 - 4440Collections
Publikationen (Experimentalphysik III - Femtosekundenspektroskopie und ultraschnelle Laserkontrolle)Citation
@article{urn:nbn:de:hebis:34-2008102924960,
author={Baumert, Thomas and Herek, Jennifer L. and Zewail, Ahmed H.},
title={Femtosecond real-time probing of reactions},
year={1993}
}
0500 Oax 0501 Text $btxt$2rdacontent 0502 Computermedien $bc$2rdacarrier 1100 1993$n1993 1500 1/eng 2050 ##0##urn:nbn:de:hebis:34-2008102924960 3000 Baumert, Thomas 3010 Herek, Jennifer L. 3010 Zewail, Ahmed H. 4000 Femtosecond real-time probing of reactions :XI. The elementary OClO fragmentation / Baumert, Thomas 4030 4060 Online-Ressource 4085 ##0##=u http://nbn-resolving.de/urn:nbn:de:hebis:34-2008102924960=x R 4204 \$dAufsatz 4170 7136 ##0##urn:nbn:de:hebis:34-2008102924960
2008-10-29T09:57:00Z 2008-10-29T09:57:00Z 1993 0021-9606 urn:nbn:de:hebis:34-2008102924960 http://hdl.handle.net/123456789/2008102924960 1260859 bytes application/pdf eng Urheberrechtlich geschützt https://rightsstatements.org/page/InC/1.0/ 530 Femtosecond real-time probing of reactions Aufsatz 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. open access XI. The elementary OClO fragmentation In: The Journal of Chemical Physics. - Woodbury, NY : AIP, 99.1993. - S. 4430 - 4440 Baumert, Thomas Herek, Jennifer L. Zewail, Ahmed H. Extern
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Urheberrechtlich geschützt