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Title: Simulating Fluorescence-Detected Two-Dimensional Electronic Spectroscopy of Multichromophoric Systems

Abstract

Here, we present a theory for modeling fluorescence-detected two-dimensional electronic spectroscopy of multichromophoric systems. The theory is tested by comparison of the predicted spectra of the light-harvesting complex LH2 with experimental data. A qualitative explanation of the strong cross-peaks as compared to conventional two-dimensional electronic spectra is given. The strong cross-peaks are attributed to the clean ground-state signal that is revealed when the annihilation of exciton pairs created on the same LH2 complex cancels oppositely signed signals from the doubly excited state. This annihilation process occurs much faster than the nonradiative relaxation. Furthermore, the line shape difference is attributed to slow dynamics, exciton delocalization within the bands, and intraband exciton–exciton annihilation. This is in line with existing theories presented for model systems. We further propose the use of time-resolved fluorescence-detected two-dimensional spectroscopy to study state-resolved exciton–exciton annihilation.

Authors:
 [1];  [2];  [2];  [3];  [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Groningen, Groningen (The Netherlands)
  2. Univ. of Michigan, Ann Arbor, MI (United States)
  3. Univ. of Glasgow, Glasgow (United Kingdom)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Photosynthetic Antenna Research Center (PARC); Washington Univ., St. Louis, MO (United States); Univ. of Groningen, Groningen (Netherlands)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Org.:
[Photosynthetic Antenna Research Center, an Energy Frontier Research Center]
OSTI Identifier:
1491256
Grant/Contract Number:  
[SC0001035]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
[ Journal Volume: 123; Journal Issue: 2]; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Kunsel, Tenzin, Tiwari, Vivek, Matutes, Yassel Acosta, Gardiner, Alastair T., Cogdell, Richard J., Ogilvie, Jennifer P., and Jansen, Thomas L. C. Simulating Fluorescence-Detected Two-Dimensional Electronic Spectroscopy of Multichromophoric Systems. United States: N. p., 2018. Web. doi:10.1021/acs.jpcb.8b10176.
Kunsel, Tenzin, Tiwari, Vivek, Matutes, Yassel Acosta, Gardiner, Alastair T., Cogdell, Richard J., Ogilvie, Jennifer P., & Jansen, Thomas L. C. Simulating Fluorescence-Detected Two-Dimensional Electronic Spectroscopy of Multichromophoric Systems. United States. doi:10.1021/acs.jpcb.8b10176.
Kunsel, Tenzin, Tiwari, Vivek, Matutes, Yassel Acosta, Gardiner, Alastair T., Cogdell, Richard J., Ogilvie, Jennifer P., and Jansen, Thomas L. C. Thu . "Simulating Fluorescence-Detected Two-Dimensional Electronic Spectroscopy of Multichromophoric Systems". United States. doi:10.1021/acs.jpcb.8b10176. https://www.osti.gov/servlets/purl/1491256.
@article{osti_1491256,
title = {Simulating Fluorescence-Detected Two-Dimensional Electronic Spectroscopy of Multichromophoric Systems},
author = {Kunsel, Tenzin and Tiwari, Vivek and Matutes, Yassel Acosta and Gardiner, Alastair T. and Cogdell, Richard J. and Ogilvie, Jennifer P. and Jansen, Thomas L. C.},
abstractNote = {Here, we present a theory for modeling fluorescence-detected two-dimensional electronic spectroscopy of multichromophoric systems. The theory is tested by comparison of the predicted spectra of the light-harvesting complex LH2 with experimental data. A qualitative explanation of the strong cross-peaks as compared to conventional two-dimensional electronic spectra is given. The strong cross-peaks are attributed to the clean ground-state signal that is revealed when the annihilation of exciton pairs created on the same LH2 complex cancels oppositely signed signals from the doubly excited state. This annihilation process occurs much faster than the nonradiative relaxation. Furthermore, the line shape difference is attributed to slow dynamics, exciton delocalization within the bands, and intraband exciton–exciton annihilation. This is in line with existing theories presented for model systems. We further propose the use of time-resolved fluorescence-detected two-dimensional spectroscopy to study state-resolved exciton–exciton annihilation.},
doi = {10.1021/acs.jpcb.8b10176},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = [2],
volume = [123],
place = {United States},
year = {2018},
month = {12}
}

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Works referencing / citing this record:

Before Förster. Initial excitation in photosynthetic light harvesting
journal, January 2019

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