Femtosecond β-cleavage dynamics: Observation of the diradical intermediate in the nonconcerted reactions of cyclic ethers
Femtosecond (fs) dynamics of reactions of cyclic ethers, symmetric and asymmetric structures, are reported. The diradical intermediates and their beta-cleavages, which involve simultaneous C-C, C-H sigma-bond breakage and C-O, C-C pi-bond formation, are observed and studied by fs-resolved mass spectrometry. To compare with experiments, we present density functional theory calculations of the potential energy surface and microcanonical rates and product distributions.
Additional Information© 1998 American Institute of Physics. Received 18 February 1998; accepted 11 March 1998. This work was supported by the Office of Naval Research and the National Science Foundation. A.A.S. would like to thank Worcester Polytechnic Institute for a sabbatical leave at Caltech.
Published - SCAjcp98.pdf