Background-free measurement of exciton-exciton annihilation by two-quantum fluorescence-detected pump-probe spectroscopy

Fuente: arXiv
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Main Authors: Jayachandran, Ajay, Mueller, Stefan, Lambert, Christoph, Brixner, Tobias
Format: Preprint
Published: 2026
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author Jayachandran, Ajay
Mueller, Stefan
Lambert, Christoph
Brixner, Tobias
author_facet Jayachandran, Ajay
Mueller, Stefan
Lambert, Christoph
Brixner, Tobias
contents We introduce two-quantum (2Q) fluorescence-detected pump-probe (F-PP) spectroscopy as a tool to probe ultrafast multiparticle interactions in many-body systems. We describe a pulse-shaper-based fully collinear setup utilizing phase cycling to capture the 2Q F-PP signal simultaneously with the one-quantum (1Q) F-PP signal. Thus, we investigate the dynamics of energy transfer and diffusion-limited annihilation. We apply a data post-processing strategy to isolate excited-state dynamics from spurious background. The technique is applied to a squaraine heterodimer and a squaraine copolymer to demonstrate the removal of so-called incoherent mixing that generally plagues action-detected nonlinear spectroscopy on multichromophoric systems. Specifically, we show that this approach is not only applicable to 1Q but also to 2Q F-PP signals, eliminating incoherent mixing contributions as well as other "parasitic" signals that result from pulse-overlap ambiguities. As a result, we retrieve background-free spectral and dynamical information of doubly excited electronic states.
format Preprint
id arxiv_https___arxiv_org_abs_2605_11984
institution arXiv
publishDate 2026
record_format arxiv
spellingShingle Background-free measurement of exciton-exciton annihilation by two-quantum fluorescence-detected pump-probe spectroscopy
Jayachandran, Ajay
Mueller, Stefan
Lambert, Christoph
Brixner, Tobias
Chemical Physics
Optics
We introduce two-quantum (2Q) fluorescence-detected pump-probe (F-PP) spectroscopy as a tool to probe ultrafast multiparticle interactions in many-body systems. We describe a pulse-shaper-based fully collinear setup utilizing phase cycling to capture the 2Q F-PP signal simultaneously with the one-quantum (1Q) F-PP signal. Thus, we investigate the dynamics of energy transfer and diffusion-limited annihilation. We apply a data post-processing strategy to isolate excited-state dynamics from spurious background. The technique is applied to a squaraine heterodimer and a squaraine copolymer to demonstrate the removal of so-called incoherent mixing that generally plagues action-detected nonlinear spectroscopy on multichromophoric systems. Specifically, we show that this approach is not only applicable to 1Q but also to 2Q F-PP signals, eliminating incoherent mixing contributions as well as other "parasitic" signals that result from pulse-overlap ambiguities. As a result, we retrieve background-free spectral and dynamical information of doubly excited electronic states.
title Background-free measurement of exciton-exciton annihilation by two-quantum fluorescence-detected pump-probe spectroscopy
topic Chemical Physics
Optics
url https://arxiv.org/abs/2605.11984