ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
The technique of H (Rydberg) atom photofragment translational spectroscopy has been used to study the process HFCO(S1)→H+FCO(X˜), near its appearance threshold, at excitation wavelengths ca. 247 nm. Analyses of the resulting total kinetic energy release spectra lead to an accurate determination of the C–H bond strength: D0(H–FCO)=34950±20 cm−1. The resulting FCO fragments are observed to be formed with little internal energy, distributed mainly in the form of a-axis rotation. Fragmentation is shown to involve S1–T1 intersystem crossing, followed by rapid passage along the minimum energy path to the eventual H+FCO products. This minimum energy path involves passage over (or H atom tunnelling through) a saddle point, the height of which is ≥4740 cm−1 above the dissociation asymptote. The observed propensity for a-axis rotation in the FCO product reflects changes in the parent geometry as it evolves along the C–H dissociation coordinate on the T1 surface; past the saddle point, the barrier energy is released largely in the form of product recoil.© 1997 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.473243
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