Geometry optimization of the ring-opened oxirane diradical: mechanism of the addition reaction of the triplet oxygen atom to olefins

Kizashi Yamaguchi, Satoshi Yabushita, Takayuki Fueno, Shigeki Kato, Keiji Morokuma

研究成果: Article査読

53 被引用数 (Scopus)

抄録

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.

本文言語English
ページ(範囲)27-30
ページ数4
ジャーナルChemical Physics Letters
70
1
DOI
出版ステータスPublished - 1980 2月 15

ASJC Scopus subject areas

  • 物理学および天文学(全般)
  • 物理化学および理論化学

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