Ultrafast Ring-Opening Reaction of 1,3-Cyclohexadiene: Identification of Nonadiabatic Pathway via Doubly Excited State

Shutaro Karashima, Alexander Humeniuk, Ryuta Uenishi, Takuya Horio, Manabu Kanno, Tetsuro Ohta, Junichi Nishitani, Roland Mitrić, Toshinori Suzuki

研究成果: Contribution to journalArticle査読

3 被引用数 (Scopus)

抄録

The photoinduced ring-opening reaction of 1,3-cyclohexadiene (CHD) to produce 1,3,5-hexatriene (HT) plays an essential role in the photobiological synthesis of vitamin D3 in the skin. This reaction follows the Woodward-Hoffmann rule, and C5-C6 bond rupture via an electronically excited state occurs with conrotatory motion of the end CH2 groups. However, it is noted that the photoexcited S1(π,π*) state of CHD is not electronically correlated with the ground state of HT, and the reaction must proceed via nonadiabatic transitions. In the present study, we have clearly observed the nonadiabatic reaction pathway via the doubly excited state of CHD using ultrafast extreme UV photoelectron spectroscopy. The results indicate that the reaction occurs in only 68 fs and creates product vibrational coherence. Extensive computational simulations support the interpretation of experimental results and provide further insights into the electronic dynamics in this paradigmatic electrocyclic ring-opening reaction.

本文言語英語
ページ(範囲)8034-8045
ページ数12
ジャーナルJournal of the American Chemical Society
143
21
DOI
出版ステータス出版済み - 6 2 2021
外部発表はい

All Science Journal Classification (ASJC) codes

  • 触媒
  • 化学 (全般)
  • 生化学
  • コロイド化学および表面化学

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