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Switching the relaxation pathway by steric effects in conjugated dienes

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Title: Switching the relaxation pathway by steric effects in conjugated dienes
Authors: Tentaku, Tateharu Browse this author
Atobe, Ryunosuke Browse this author
Tsutsumi, Takuro Browse this author →KAKEN DB
Satoh, Sota Browse this author
Harabuchi, Yu Browse this author →KAKEN DB
Taketsugu, Tetsuya Browse this author →KAKEN DB
Sekikawa, Taro Browse this author →KAKEN DB
Issue Date: 6-Oct-2021
Publisher: IOP Publishing
Journal Title: Journal of Physics B : Atomic, Molecular and Optical Physics
Volume: 54
Issue: 17
Start Page: 174004
Publisher DOI: 10.1088/1361-6455/ac274c
Abstract: 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.
Rights: 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
Type: article (author version)
Appears in Collections:工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 関川 太郎

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