Geometry optimizations of several low-lying diradical states of the ring-opened oxirane (·CH2CH2O·) were performed by using the energy gradients of the UHF MINDO/3, STO-3G and 4-31G solutions. Both the STO-3G and 4-3 IG methods predict that the most stable form is the triplet state of the non-twisted σπ conformation in which the unpaired spins localized on the terminal carbon and oxygen atoms are oriented perpendicularly to each other. The singlet σσ diradical state in which both the radical-site p orbitals are coplanar with the molecular framework is only 2.3 (STO-3G) and 1.2 (4-31G) kcal/mol less stable than the triplet σπ diradical state. It is found that the geometry of the singlet σσ diradical is unique in that the C-C-O angle is noticeably small as compared with various other diradical states. Implications of these results to the mechanism of the oxirane-forming O(3P) + C2H4 reaction are discussed.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry