Aa. Scala et al., FEMTOSECOND BETA-CLEAVAGE DYNAMICS - OBSERVATION OF THE DIRADICAL INTERMEDIATE IN THE NONCONCERTED REACTIONS OF CYCLIC ETHERS, The Journal of chemical physics, 108(19), 1998, pp. 7933-7936
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 b
reakage and C-O, C-C pi-bond formation, are observed and studied by fs
-resolved mass spectrometry. To compare with experiments, we present d
ensity functional theory calculations of the potential energy surface
and microcanonical rates and product distributions. (C) 1998 American
Institute of Physics.