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Updated: Dec 25, 2025

Ultrafast Time-resolved Near-IR Stimulated Raman Measurements of Functional π-conjugate Systems
Published on: February 10, 2020
Tracking Structural Evolution during Symmetry-Breaking Charge Separation in Quadrupolar Perylene Bisimide with
Woojae Kim1, Taeyeon Kim1, Seongsoo Kang1
1Department of Chemistry, Spectroscopy Laboratory for Functional π-Electronic Systems, Yonsei University, 03722, Seoul, Korea.
Abstract:
Elucidating structural roles in photoinduced charge transfer is indispensable, as nuclear rearrangements are simultaneously usually involved in the dynamics. However, it is hard to evaluate whether the structural changes occur or not by using conventional time-resolved electronic spectroscopy. Here, time-resolved impulsive stimulated Raman spectroscopy is applied to record the evolution of vibrational snapshots during charge-separation dynamics of donor-acceptor-donor-type quadrupolar perylene bisimide in real time. Drastic frequency shifts were observed for several Raman bands with their population kinetics, thus symmetry-breaking charge separation accompanies significant structural changes, as supported by (TD)-DFT calculations. A comparison between time-resolved Raman spectra of the neutral S1 state and the radical anion species shows that the spectral signatures, especially in high-frequency regions, provide important clues to bond length alternation patterns in the PBI core.
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