Quasiperiodic trajectories in the unimolecular dissociation of ethyl radicals by time-frequency analysis

Direct classical trajectory calculations for ethyl radical, C 2 H 5 , at the HCTH147@ 6 - 31 + G * * ∕ 6 - 31 G * * level of theory support the experimental observation that the dissociation of highly excited ethyl radicals to ethylene and and a hydrogen atom can occur much more slowly than predicte...

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Published in:The Journal of chemical physics 2005-07, Vol.123 (2), p.021101-021101-4
Main Authors: Bach, Andreas, Hostettler, Jonas M., Chen, Peter
Format: Article
Language:English
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Summary:Direct classical trajectory calculations for ethyl radical, C 2 H 5 , at the HCTH147@ 6 - 31 + G * * ∕ 6 - 31 G * * level of theory support the experimental observation that the dissociation of highly excited ethyl radicals to ethylene and and a hydrogen atom can occur much more slowly than predicted by statistical rate theories. Only 78% of the trajectories of ethyl radicals prepared in a microcanonical ensemble with 120 - kcal ∕ mol excitation energy above the zero-point energy and zero total angular momentum dissociate to form C 2 H 4 + H . The remaining hot ground-state ethyl radicals have a lifetime of ⪢ 2 ps , during which a time-frequency analysis finds them trapped for extended periods of time in long-lived quasiperiodic trajectories.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.1950673