We theoretically investigated the effect of mixed Frenkel (F) and charge transfer (CT) states on the spectral properties of perylene bisimide (PBI) derivatives, focusing on the role of strong electron–phonon interactions. The model consists of a four-level system described by the Holstein Hamiltonian coupled to independent local heat-baths on each site, described by Brownian spectral distribution functions. We employ the reduced hierarchical equations of motion (HEOM) approach to calculate the time evolution of the system and compare it to the pure F exciton cases. We compute the absorption and time-gated fluorescence (TGF) spectra for different exciton transfer integrals and F-CT bandgap conditions. The coherence length of excitons (Ncoh) is evaluated employing two different definitions. We observe the presence of an excited hot state peak whose intensity is associated with the delocalization of the excited species and ultrafast dynamics that are solely dependent on the frequency of the local bath. The results indicate that the inclusion of CT states promotes localization of the excitons, which is manifested in a decrease in the intensity of the hot state peak and the 0–1 peak and an increase in the intensity of the 0–0 emission peak in the TGF spectrum, leading to a decrease of Ncoh.
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28 August 2022
Research Article|
August 22 2022
Effect of mixed Frenkel and charge transfer states in time-gated fluorescence spectra of perylene bisimides H-aggregates: Hierarchical equations of motion approach
Special Collection:
Photophysics in Emerging Photovoltaics
Mauro Cainelli
;
Mauro Cainelli
a)
(Conceptualization, Data curation, Formal analysis, Investigation, Methodology, Software, Writing – original draft)
1
Department of Chemistry, Graduate School of Science, Kyoto University
, Kyoto 606-8502, Japan
a)Authors to whom correspondence should be addressed: cainelli.mauro@gmail.com; raffaele.borrelli@unito.it; and tanimura.yoshitaka.5w@kyoto-u.jp
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Raffaele Borrelli
;
Raffaele Borrelli
a)
(Conceptualization, Formal analysis, Investigation, Project administration, Writing – review & editing)
1
Department of Chemistry, Graduate School of Science, Kyoto University
, Kyoto 606-8502, Japan
2
DISAFA, University of Torino
, Largo Paolo Braccini 2, I-10095 Grugliasco, Italy
a)Authors to whom correspondence should be addressed: cainelli.mauro@gmail.com; raffaele.borrelli@unito.it; and tanimura.yoshitaka.5w@kyoto-u.jp
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Yoshitaka Tanimura
Yoshitaka Tanimura
a)
(Funding acquisition, Investigation, Methodology, Project administration, Resources, Writing – review & editing)
1
Department of Chemistry, Graduate School of Science, Kyoto University
, Kyoto 606-8502, Japan
a)Authors to whom correspondence should be addressed: cainelli.mauro@gmail.com; raffaele.borrelli@unito.it; and tanimura.yoshitaka.5w@kyoto-u.jp
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a)Authors to whom correspondence should be addressed: cainelli.mauro@gmail.com; raffaele.borrelli@unito.it; and tanimura.yoshitaka.5w@kyoto-u.jp
Note: This paper is part of the JCP Special Topic on Photophysics in Emerging Photovoltaics.
J. Chem. Phys. 157, 084103 (2022)
Article history
Received:
June 06 2022
Accepted:
July 21 2022
Citation
Mauro Cainelli, Raffaele Borrelli, Yoshitaka Tanimura; Effect of mixed Frenkel and charge transfer states in time-gated fluorescence spectra of perylene bisimides H-aggregates: Hierarchical equations of motion approach. J. Chem. Phys. 28 August 2022; 157 (8): 084103. https://doi.org/10.1063/5.0102000
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