ABINITIO SCF CALCULATIONS ON THE PHOTO-CHEMICAL BEHAVIOR OF THE 3-MEMBERED RINGS .4. OXIRANE - FRAGMENTATION

The complete evolution of ethylene oxide by monomolecular processes is theoretically simulated according to the reactive scheme designed in the preceding paper. Various pathways are examined describing the most usual fragmentations : formation of ethylene and atomic oxygen in one-and two-step processes; formation of carbene and formaldehyde by direct two-bond scission or from evolution of intermediates I and II by CC and CO bond ruptures, respectively; acetaldehyde formation by hydrogen migration from intermediate I. A semiquantitative rationale is proposed for the overall thermal reactivity and the photochemical behavior in the first accessible singlet and triplet valence excited states. © 1979, American Chemical Society. All rights reserved.