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Main Authors: Zheng, Yulong, Rojas-Gatjens, Esteban, Lee, Myeongyeon, Reichmanis, Elsa, Silva-Acuña, Carlos
Format: Preprint
Published: 2024
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Online Access:https://arxiv.org/abs/2401.04035
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author Zheng, Yulong
Rojas-Gatjens, Esteban
Lee, Myeongyeon
Reichmanis, Elsa
Silva-Acuña, Carlos
author_facet Zheng, Yulong
Rojas-Gatjens, Esteban
Lee, Myeongyeon
Reichmanis, Elsa
Silva-Acuña, Carlos
contents Bound and unbound Frenkel-exciton pairs are essential transient precursors for a variety of photophysical and biochemical processes. In this work, we identify bound and unbound {Frenkel}-exciton complexes in an electron push-pull polymer semiconductor using coherent two-dimensional spectroscopy. We find that the dominant $A_{0-1}$ peak of the absorption vibronic progression is accompanied by a sub-peak, each dressed by distinct vibrational modes. By considering the Liouville pathways within a two-exciton model, the imbalanced cross peaks in one-quantum rephasing and non-rephasing spectra can be accounted for by the presence of pure biexcitons. The two-quantum non-rephasing spectra, on the other hand, provide direct evidence for unbound exciton pairs and biexcitons with dominantly attractive force. In addition, the spectral features of unbound exciton pairs show mixed absorptive and dispersive character, implying many-body interactions within the correlated {Frenkel}-exciton pairs. Our work offers novel perspectives on the rich photophysical processes in semiconductor polymers with the presence of Frenkel exciton complexes.
format Preprint
id arxiv_https___arxiv_org_abs_2401_04035
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Unveiling multi-quantum excitonic correlations in push-pull polymer semiconductors
Zheng, Yulong
Rojas-Gatjens, Esteban
Lee, Myeongyeon
Reichmanis, Elsa
Silva-Acuña, Carlos
Materials Science
Chemical Physics
Bound and unbound Frenkel-exciton pairs are essential transient precursors for a variety of photophysical and biochemical processes. In this work, we identify bound and unbound {Frenkel}-exciton complexes in an electron push-pull polymer semiconductor using coherent two-dimensional spectroscopy. We find that the dominant $A_{0-1}$ peak of the absorption vibronic progression is accompanied by a sub-peak, each dressed by distinct vibrational modes. By considering the Liouville pathways within a two-exciton model, the imbalanced cross peaks in one-quantum rephasing and non-rephasing spectra can be accounted for by the presence of pure biexcitons. The two-quantum non-rephasing spectra, on the other hand, provide direct evidence for unbound exciton pairs and biexcitons with dominantly attractive force. In addition, the spectral features of unbound exciton pairs show mixed absorptive and dispersive character, implying many-body interactions within the correlated {Frenkel}-exciton pairs. Our work offers novel perspectives on the rich photophysical processes in semiconductor polymers with the presence of Frenkel exciton complexes.
title Unveiling multi-quantum excitonic correlations in push-pull polymer semiconductors
topic Materials Science
Chemical Physics
url https://arxiv.org/abs/2401.04035