Dynamic Effects on the Product Distribution of the Photoreaction of <i>s</i>-<i>cis</i>-1,3-Butadiene: A Nonadiabatic Molecular Dynamics Study

• Toshiaki Matsubara

  Department of Chemistry, Faculty of Science, Kanagawa University, 2946 Tsuchiya, Hiratsuka, Kanagawa 259-1293 , Japan

抄録

A dynamic factor that determines the product distribution of the photochemical reaction of S2-excited s-cis-1,3-butadiene is examined using the nonadiabatic molecular dynamics method. The excited S2 state of s-cis-1,3-butadiene is relaxed via the S2/S1 and subsequent S1/S0 conical intersections (CIs). After the S1/S0-CI, several products including the trans and cis isomers, cyclobutene, bicyclobutane, and the methylenecyclopropyl diradical, are generated by six identified reaction channels. Channel 6 is another new channel leading to bicyclobutane. The ratio of each product is understood in terms of the allowed range of the ∠C–C–C–C dihedral angle at the S1/S0-CI for each product. When 2,3-dimethyl-1,3-butadiene is used instead of 1,3-butadiene, the product ratio changes because due to the dynamic effects of the Me groups the rotational motion around the central C–C bond slows down and consequently the fluctuation of the ∠C–C–C–C dihedral angle at the S1/S0-CI becomes smaller. Thus, our molecular dynamics simulations show that the fluctuation of the ∠C–C–C–C dihedral angle is an important factor to determine the product distribution.

収録刊行物

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 94 (6), 1720-1727, 2021-04-27

  Oxford University Press (OUP)

キーワード

• General Chemistry

詳細情報

• CRID: 1360851717628246400
• NII論文ID: 130008066548
• DOI: 10.1246/bcsj.20210069
• ISSN: 13480634
• ISSN: 00092673
• Web Site: https://academic.oup.com/bcsj/article-pdf/94/6/1720/56310125/bcsj.20210069.pdf
• データソース種別:
  • Crossref
  • CiNii Articles
  • KAKEN