Broadband Transient Fluorescence Reveals a Two-State Picture of Peridinin
7 affiliations
- 1Department of Chemistry, Professorship of Dynamic Spectroscopy, TUM School of Natural Sciences, Technical University of Munich, 85748 Garching, Germany
- 2Department of Chemistry and Centre for NanoScience, Ludwig-Maximilians-Universität München, 81377 München, Germany
- 3Laboratory of Soft Matter Physics, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
- 4School of Physical Science, University of the Chinese Academy of Sciences, Beijing 100049, China
- 5Faculty of Mathematics and Physics, Charles University, 113 36 Prague, Czech Republic
- 6Biophysics, Department of Biology and Biotechnology, Ruhr-University Bochum, 44780 Bochum, Germany
- 7Institut für Chemie und Biochemie, Freie Universität Berlin, 14195 Berlin, Germany
Abstract
Peridinin is a light-harvesting apocarotenoid whose excited-state relaxation is often described by population transfer among 1Bu, 2Ag, and intramolecular charge-transfer states. Here broadband-detected transient fluorescence reveals a simpler picture for peridinin in ethylene glycol. Following optical excitation, we observe instantaneous blue-green emission from the bright 1Bu state that depopulates with a 150 fs time constant and directly gives rise to weak red emission from the lowest 2Ag state, which decays in 12 ps. The presence of an isosbestic point and the absence of additional fluorescence components indicate direct internal conversion without a resolvable hot S1 or a separate equilibration process involving a charge-transfer state. XMS-RASPT2 and DFT/MRCI calculations reproduce this behavior by showing strong displacement of the 1Bu and 2Ag minima from the Franck–Condon region and weak oscillator strength at the relaxed 2Ag minimum. The results identify peridinin as an emitter from its 1Bu and 2Ag states and revise the interpretation of its charge-transfer-like signatures.
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BibTeX
@article{bach2026broadband,
title = {{Broadband Transient Fluorescence Reveals a Two-State Picture of Peridinin}},
author = {Alina Bach and Constantin Jaschke and Heyuan Liu and Hailong Chen and Erika Keil and Eckhard Hofmann and Yuxiang Weng and Jan P. Götze and Benjamin P. Fingerhut and Jürgen Hauer},
journal = {The Journal of Physical Chemistry Letters},
year = {2026},
month = oct,
doi = {10.1021/acs.jpclett.6c02559},
url = {https://doi.org/10.1021/acs.jpclett.6c02559},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Broadband Transient Fluorescence Reveals a Two-State Picture of Peridinin
AU - Alina Bach
AU - Constantin Jaschke
AU - Heyuan Liu
AU - Hailong Chen
AU - Erika Keil
AU - Eckhard Hofmann
AU - Yuxiang Weng
AU - Jan P. Götze
AU - Benjamin P. Fingerhut
AU - Jürgen Hauer
PY - 2026
DA - 2026/10/14
JO - The Journal of Physical Chemistry Letters
DO - 10.1021/acs.jpclett.6c02559
UR - https://doi.org/10.1021/acs.jpclett.6c02559
AB - Peridinin is a light-harvesting apocarotenoid whose excited-state relaxation is often described by population transfer among 1Bu, 2Ag, and intramolecular charge-transfer states. Here broadband-detected transient fluorescence reveals a simpler picture for peridinin in ethylene glycol. Following optical excitation, we observe instantaneous blue-green emission from the bright 1Bu state that depopulates with a 150 fs time constant and directly gives rise to weak red emission from the lowest 2Ag state, which decays in 12 ps. The presence of an isosbestic point and the absence of additional fluorescence components indicate direct internal conversion without a resolvable hot S1 or a separate equilibration process involving a charge-transfer state. XMS-RASPT2 and DFT/MRCI calculations reproduce this behavior by showing strong displacement of the 1Bu and 2Ag minima from the Franck–Condon region and weak oscillator strength at the relaxed 2Ag minimum. The results identify peridinin as an emitter from its 1Bu and 2Ag states and revise the interpretation of its charge-transfer-like signatures.
SN - 1948-7185
ER -