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Updated: Apr 5, 2026

Ultrafast Time-resolved Near-IR Stimulated Raman Measurements of Functional π-conjugate Systems
Published on: February 10, 2020
Ultrafast Relaxation Dynamics in trans-1,3-Butadiene Studied by Time-Resolved Photoelectron Spectroscopy with High
Ayumu Makida1, Hironori Igarashi1, Takehisa Fujiwara1
1†Department of Applied Physics, Faculty of Engineering, Hokkaido University, Kita 13 Nishi 8, Kita-ku, Sapporo 060-8628, Japan.
Abstract:
In trans-1,3-butadiene, the ultrafast relaxation from the doubly excited state 2(1)Ag and the corresponding recovery of the ground state 1(1)Ag were observed simultaneously for the first time by time-resolved photoelectron spectroscopy (TRPES) using 29.5 eV high harmonic pulses. The fast recovery of 1(1)Ag shows that the following dissociation upon photoexcitation takes place after returning to the ground state. At 427 fs after photoexcitation, only the ionization energy from the C═C σ bond was found to remain shifted. Accompanying theoretical calculations with an assumption of Koopmans' theorem show that the ionization energy of the C═C σ bond is modulated by vibrational excitation of the antisymmetric C═C stretching mode. TRPES by high harmonics can probe the changes in the molecular structure sensitively.
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