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Title: Before Förster. Initial excitation in photosynthetic light harvesting

Abstract

Electronic 2D spectroscopy allows nontrivial quantum effects to be explored in unprecedented detail. Here, we apply recently developed fluorescence detected coherent 2D spectroscopy to study the light harvesting antenna 2 (LH2) of photosynthetic purple bacteria. We report double quantum coherence 2D spectra which show clear cross peaks indicating correlated excitations. Similar results are found for rephasing and nonrephasing signals. Analysis of signal generating quantum pathways leads to the conclusion that, contrary to the currently prevailing physical picture, the two weakly coupled pigment rings of LH2 share the initial electronic excitation leading to quantum mechanical correlation between the two clearly separate absorption bands. These results are general and have consequences for the interpretation of initially created excited states not only in photosynthesis but in all light absorbing systems composed of weakly interacting pigments where the excitation transfer is commonly described by using Förster theory. Being able to spectrally resolve the nonequilibrium dynamics immediately following photoabsorption may provide a glimpse to the systems' transition into the Förster regime.

Authors:
ORCiD logo [1];  [1];  [2];  [1]; ORCiD logo [3];  [4];  [3]; ORCiD logo [1]
  1. Chemical Physics and NanoLund, Lund University, 22100 Lund, Sweden
  2. Institute of Industrial Science, The University of Tokyo, Tokyo 153-8505, Japan
  3. Institute of Molecular, Cell and Systems Biology, College of Medical, Veterinary and Life Sciences, University of Glasgow, Glasgow G12 8QQ, UK
  4. Institute of Physics, University of Rostock, 18059 Rostock, Germany
Publication Date:
Research Org.:
Washington Univ., St. Louis, MO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Lundbeck Foundation; Swedish Research Council (VR); Knut and Alice Wallenberg Foundation; Swedish Energy Agency; Crafoord Foundation; Scandinavia-Japan Sasakawa Foundation
OSTI Identifier:
1542487
Alternate Identifier(s):
OSTI ID: 1610496
Grant/Contract Number:  
SC0001035
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 10 Journal Issue: 34; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry

Citation Formats

Karki, Khadga J., Chen, Junsheng, Sakurai, Atsunori, Shi, Qi, Gardiner, Alastair T., Kühn, Oliver, Cogdell, Richard J., and Pullerits, Tönu. Before Förster. Initial excitation in photosynthetic light harvesting. United Kingdom: N. p., 2019. Web. https://doi.org/10.1039/C9SC01888C.
Karki, Khadga J., Chen, Junsheng, Sakurai, Atsunori, Shi, Qi, Gardiner, Alastair T., Kühn, Oliver, Cogdell, Richard J., & Pullerits, Tönu. Before Förster. Initial excitation in photosynthetic light harvesting. United Kingdom. https://doi.org/10.1039/C9SC01888C
Karki, Khadga J., Chen, Junsheng, Sakurai, Atsunori, Shi, Qi, Gardiner, Alastair T., Kühn, Oliver, Cogdell, Richard J., and Pullerits, Tönu. Wed . "Before Förster. Initial excitation in photosynthetic light harvesting". United Kingdom. https://doi.org/10.1039/C9SC01888C.
@article{osti_1542487,
title = {Before Förster. Initial excitation in photosynthetic light harvesting},
author = {Karki, Khadga J. and Chen, Junsheng and Sakurai, Atsunori and Shi, Qi and Gardiner, Alastair T. and Kühn, Oliver and Cogdell, Richard J. and Pullerits, Tönu},
abstractNote = {Electronic 2D spectroscopy allows nontrivial quantum effects to be explored in unprecedented detail. Here, we apply recently developed fluorescence detected coherent 2D spectroscopy to study the light harvesting antenna 2 (LH2) of photosynthetic purple bacteria. We report double quantum coherence 2D spectra which show clear cross peaks indicating correlated excitations. Similar results are found for rephasing and nonrephasing signals. Analysis of signal generating quantum pathways leads to the conclusion that, contrary to the currently prevailing physical picture, the two weakly coupled pigment rings of LH2 share the initial electronic excitation leading to quantum mechanical correlation between the two clearly separate absorption bands. These results are general and have consequences for the interpretation of initially created excited states not only in photosynthesis but in all light absorbing systems composed of weakly interacting pigments where the excitation transfer is commonly described by using Förster theory. Being able to spectrally resolve the nonequilibrium dynamics immediately following photoabsorption may provide a glimpse to the systems' transition into the Förster regime.},
doi = {10.1039/C9SC01888C},
journal = {Chemical Science},
number = 34,
volume = 10,
place = {United Kingdom},
year = {2019},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/C9SC01888C

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Cited by: 8 works
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    Works referencing / citing this record:

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