Switching the relaxation pathway by steric effects in conjugated dienes

Tentaku, Tateharu; Atobe, Ryunosuke; Tsutsumi, Takuro; Satoh, Sota; Harabuchi, Yu; Taketsugu, Tetsuya; Sekikawa, Taro

Switching the relaxation pathway by steric effects in conjugated dienes

Tentaku, Tateharu; Atobe, Ryunosuke; Tsutsumi, Takuro et al.

Journal of Physics B : Atomic, Molecular and Optical Physics, 2021, 54(17), 174004

Permalink : https://hdl.handle.net/2115/86907

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アクセス権	open access
URI	https://hdl.handle.net/2115/86907
タイトル	Switching the relaxation pathway by steric effects in conjugated dienes
著者	Tentaku, Tateharu ; Atobe, Ryunosuke ; Tsutsumi, Takuro ; Satoh, Sota ; Harabuchi, Yu ; Taketsugu, Tetsuya ; Sekikawa, Taro
著者名 Tentaku, Tateharu
著者名 Atobe, Ryunosuke
e-Rad_Researcher 80930437 著者名 Tsutsumi, Takuro
著者名 Satoh, Sota
e-Rad_Researcher 60727204 著者名 Harabuchi, Yu
e-Rad_Researcher 90280932 著者名 Taketsugu, Tetsuya
e-Rad_Researcher 90282607 著者名 Sekikawa, Taro
言語	英語
発行日	2021-10-06
出版者	IOP Publishing
収録物名	Journal of Physics B : Atomic, Molecular and Optical Physics
巻(号)	54(17)
ページ	174004
抄録	Modification of a molecular structure at the minimum-energy conical intersection (MECI) on the relaxation pathway of the smallest conjugated polyene, trans-1,3-butadiene (BD), was achieved by substituting the hydrogen atoms at the end of the molecular chain with methyl groups. At the MECI between S1 and S0, BD is known to have a pyramidalized structure; therefore, the substituted methyl groups are expected to hinder this pyramidalization and change the relaxation pathway. Here, the relaxation dynamics of three conjugated dienes: BD, trans-1,3-pentadiene (PD), and 2,5-dimethyl-2,4-hexadiene (HD), were investigated by time-resolved photoelectron spectroscopy (TRPES) using single-order high harmonic pulses. Ultrafast relaxation to the ground state with decay times of less than 100 fs was observed in all three molecules. The potential energy curves from the theoretical calculation show the common features among these dienes, which explains the similar relaxation dynamics. However, HD was found theoretically to have a transoid structure at MECI between S1 and S0, while BD and PD both had pyramidalized structures. The relaxation pathway switching was corroborated experimentally by analysis of the photoelectron spectra specifically appearing in HD after a few hundred femtoseconds upon photoexcitation. The larger twist in the transoid structure stimulates molecular vibrations that modulated the photoionization probabilities.
資源タイプ	学術雑誌論文
出版タイプ	Accepted Manuscript
権利情報	Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported
権利情報	This is the Accepted Manuscript version of an article accepted for publication in Journal of Physics B: Atomic, Molecular and Optical Physics. IOP Publishing Ltd is not responsible for any errors or omissions in this version of the manuscript or any version derived from it. The Version of Record is available online at https://doi.org/10.1088/1361-6455/ac274c.
PISSN	0953-4075
NCID	AA10693237
関連情報 (isVersionOf)	出版社版DOI https://doi.org/10.1088/1361-6455/ac274c