Femtosecond dynamics of hydrogen elimination: benzene formation from cyclohexadiene
Using femtosecond-resolved mass spectrometry in a molecular beam, we report real-time study of the hydrogen elimination reaction of 1,4-cyclohexadiene. The experimental observation of the ultrafast stepwise H-elimination elucidates the reaction dynamics and mechanism. With density-functional theory (ground-state) calculations, the nature of the reaction (multiple) pathways is examined. With the help of recent conical-intersection calculations, the excited-state and ground-state pathways are correlated. From these experimental and theoretical results we provide a unifying picture of the thermochemistry, photochemistry and the stereochemistry observed in the condensed phase.
Additional Information© Royal Society of Chemistry 2000; © The Owner Societies 2000. Received 4th October 1999, Accepted 17th January 2000, Published on the Web 7th February 2000. This work was supported by the National Science Foundation, the Office of Naval Research, and the Air Force Office of Scientific Research. We thank Professor K. N. Houk and Dr Sarah Wilsey for many helpful correspondences. SDF, a postdoctoral fellow of the Fund for Scientific Research-Flanders, acknowledges a Fulbright scholarship and financial support by the Katholieke Universiteit Leuven and by Caltech.
Published - FEYpccp00.pdf