Spectro-temporal symmetry in action-detected optical spectroscopy: Highlighting excited-state dynamics in large systems
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F25%3A10500246" target="_blank" >RIV/00216208:11320/25:10500246 - isvavai.cz</a>
Result on the web
<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=ybltVuycwk" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=ybltVuycwk</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1063/5.0255316" target="_blank" >10.1063/5.0255316</a>
Alternative languages
Result language
angličtina
Original language name
Spectro-temporal symmetry in action-detected optical spectroscopy: Highlighting excited-state dynamics in large systems
Original language description
Multidimensional optical spectroscopy observes transient excitation dynamics through time evolution of spectral correlations. Its action-detected variants offer several advantages over the coherent detection and are thus becoming increasingly widespread. Nevertheless, a drawback of action-detected spectra is the presence of a stationary background of the so-called incoherent mixing of excitations from independent states that resembles a product of ground-state absorption spectra and obscures the excited-state signal. This issue is especially problematic in fluorescence-detected two-dimensional electronic spectroscopy (F-2DES) and fluorescence-detected pump-probe spectroscopy (F-PP) of extended systems, where large incoherent mixing arises from efficient exciton-exciton annihilation. In this work, we demonstrate on the example of F-2DES and F-PP an inherent spectro-temporal symmetry of action-detected spectra, which allows general, system-independent subtraction of any stationary signals including incoherent mixing. We derive the expressions for spectra with normal and reversed time ordering of the pulses, relating these to the symmetry of the system response. As we show both analytically and numerically, the difference signal constructed from spectra with normal and reversed pulse ordering is free of incoherent mixing and highlights the excited-state dynamics. We further verify the approach on the experimental F-PP spectra of a molecular squaraine heterodimer and the F-2DES spectra of the photosynthetic antenna light-harvesting complex 2 of purple bacteria. The approach is generally applicable to action-detected 2DES and pump-probe spectroscopy without experimental modifications and is independent of the studied system, enabling their application to large systems such as molecular complexes. (c) 2025 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license(https://creativecommons.org/licenses/by/4.0/).
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10301 - Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)
Result continuities
Project
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Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2025
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Chemical Physics
ISSN
0021-9606
e-ISSN
1089-7690
Volume of the periodical
162
Issue of the periodical within the volume
12
Country of publishing house
US - UNITED STATES
Number of pages
11
Pages from-to
124204
UT code for WoS article
001456931700005
EID of the result in the Scopus database
2-s2.0-105001662381