Simulating spectrally resolved exciton--exciton-interaction pump--probe spectroscopy
Abstract
Exciton--exciton-interaction pump--probe spectroscopy (EEI--PP) captures the fifth-order signal of light-matter interaction, directly probing exciton--exciton annihilation. This allows studying excitation energy transport even in extended, nearly isoenergetic landscapes. Although spectrally resolved fifth-order signals have already been explored in simplified cases, in larger systems only spectrally integrated signals have been analyzed. We present a microscopic theoretical description for spectrally resolved EEI--PP response with realistic lineshapes, revealing how single- and multi-exciton state structure shape the spectral features and dynamics. The description is applicable to large molecular systems such as squaraine polymers, facilitating a direct comparison with experimental spectra. By a decomposition of the total signal into individual excitation pathways, we demonstrate that the spectral resolution is needed to distinguish otherwise intertwined single- and multi-exciton dynamics, such as single-exciton relaxation and exciton--exciton annihilation.
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BibTeX
@misc{charvatova2026simulating,
title = {{Simulating spectrally resolved exciton--exciton-interaction pump--probe spectroscopy}},
author = {Kateřina Charvátová and Matteo Bruschi and Pavel Malý},
howpublished = {arXiv},
year = {2026},
month = aug,
doi = {10.48550/arxiv.2608.29041},
eprint = {2608.29041},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2608.29041},
note = {CC BY 4.0},
}
RIS
TY - UNPB
TI - Simulating spectrally resolved exciton--exciton-interaction pump--probe spectroscopy
AU - Kateřina Charvátová
AU - Matteo Bruschi
AU - Pavel Malý
PY - 2026
DA - 2026/08/29
PB - arXiv
DO - 10.48550/arxiv.2608.29041
UR - https://arxiv.org/abs/2608.29041
AB - Exciton--exciton-interaction pump--probe spectroscopy (EEI--PP) captures the fifth-order signal of light-matter interaction, directly probing exciton--exciton annihilation. This allows studying excitation energy transport even in extended, nearly isoenergetic landscapes. Although spectrally resolved fifth-order signals have already been explored in simplified cases, in larger systems only spectrally integrated signals have been analyzed. We present a microscopic theoretical description for spectrally resolved EEI--PP response with realistic lineshapes, revealing how single- and multi-exciton state structure shape the spectral features and dynamics. The description is applicable to large molecular systems such as squaraine polymers, facilitating a direct comparison with experimental spectra. By a decomposition of the total signal into individual excitation pathways, we demonstrate that the spectral resolution is needed to distinguish otherwise intertwined single- and multi-exciton dynamics, such as single-exciton relaxation and exciton--exciton annihilation.
ER -