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Title: Vibronic mixing enables ultrafast energy flow in light-harvesting complex II

Abstract

Since the discovery of quantum beats in the two-dimensional electronic spectra of photosynthetic pigment-protein complexes over a decade ago, the origin and mechanistic function of these beats in photosynthetic light-harvesting has been extensively debated. The current consensus is that these long-lived oscillatory features likely result from electronic-vibrational mixing, however, it remains uncertain if such mixing significantly influences energy transport. Here, we examine the interplay between the electronic and nuclear degrees of freedom (DoF) during the excitation energy transfer (EET) dynamics of light-harvesting complex II (LHCII) with two-dimensional electronic-vibrational spectroscopy. Particularly, we show the involvement of the nuclear DoF during EET through the participation of higher-lying vibronic chlorophyll states and assign observed oscillatory features to specific EET pathways, demonstrating a significant step in mapping evolution from energy to physical space. These frequencies correspond to known vibrational modes of chlorophyll, suggesting that electronic-vibrational mixing facilitates rapid EET over moderately size energy gaps.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2];  [1]
+ Show Author Affiliations
  1. Univ. of California, Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
OSTI Identifier:
1631639
Grant/Contract Number:  
AC02-05CH11231; DGE1752814
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 11; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; photochemistry; physical chemistry

Citation Formats

Arsenault, Eric A., Yoneda, Yusuke, Iwai, Masakazu, Niyogi, Krishna K., and Fleming, Graham R. Vibronic mixing enables ultrafast energy flow in light-harvesting complex II. United States: N. p., 2020. Web. doi:10.1038/s41467-020-14970-1.
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Arsenault, Eric A., Yoneda, Yusuke, Iwai, Masakazu, Niyogi, Krishna K., & Fleming, Graham R. Vibronic mixing enables ultrafast energy flow in light-harvesting complex II. United States. https://doi.org/10.1038/s41467-020-14970-1
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Arsenault, Eric A., Yoneda, Yusuke, Iwai, Masakazu, Niyogi, Krishna K., and Fleming, Graham R. Thu . "Vibronic mixing enables ultrafast energy flow in light-harvesting complex II". United States. https://doi.org/10.1038/s41467-020-14970-1. https://www.osti.gov/servlets/purl/1631639.
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@article{osti_1631639,
title = {Vibronic mixing enables ultrafast energy flow in light-harvesting complex II},
author = {Arsenault, Eric A. and Yoneda, Yusuke and Iwai, Masakazu and Niyogi, Krishna K. and Fleming, Graham R.},
abstractNote = {Since the discovery of quantum beats in the two-dimensional electronic spectra of photosynthetic pigment-protein complexes over a decade ago, the origin and mechanistic function of these beats in photosynthetic light-harvesting has been extensively debated. The current consensus is that these long-lived oscillatory features likely result from electronic-vibrational mixing, however, it remains uncertain if such mixing significantly influences energy transport. Here, we examine the interplay between the electronic and nuclear degrees of freedom (DoF) during the excitation energy transfer (EET) dynamics of light-harvesting complex II (LHCII) with two-dimensional electronic-vibrational spectroscopy. Particularly, we show the involvement of the nuclear DoF during EET through the participation of higher-lying vibronic chlorophyll states and assign observed oscillatory features to specific EET pathways, demonstrating a significant step in mapping evolution from energy to physical space. These frequencies correspond to known vibrational modes of chlorophyll, suggesting that electronic-vibrational mixing facilitates rapid EET over moderately size energy gaps.},
doi = {10.1038/s41467-020-14970-1},
journal = {Nature Communications},
number = 1,
volume = 11,
place = {United States},
year = {2020},
month = {3}
}
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https://doi.org/10.1038/s41467-020-14970-1
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