Julianna A. Altmann

An abinitio study of the rearrangement of carbonyl compounds to oxacarbenes

As the first part of a systematic theoretical study of oxacarbene rearrangement, ab initio SCF MO calculations employing a split valence shell basis set have been carried out for the model conversion of formaldehyde to the corresponding oxacarbene. The various cross‐sections of the reaction hypersurface were obtained by complete geometry optimization. The results suggest that, at least for the present model system, the reaction takes place preferentially in the first triplet (T1) state via a concerted pathway.

An ab initio study of the structures of ethylidene

Abstract Ab initio calculations have been carried out in order to investigate the ground state (S O ) structure of ethylidene (CH 3 -CH). Results of the complete geometry optimization suggest that ethylidene has a classical staggered geometry. Attempted geometry of optimization of the cyclic “non-classical” alternative, suggested recently by Gordon et al. was unsuccessful, since it rapidly converges to the classical structure. Some aspects of the electronic mechanism of the rearrangement of ethylidene to ethylene are also discussed.