It has long been recognized that visible light harvesting in Peridinin–Chlorophyll–Protein is driven by the interplay between the bright (S2) and dark (S1) states of peridinin (carotenoid), along with the lowest-lying bright (Qy) and dark (Qx) states of chlorophyll-a. Here, we analyse a chromophore cluster in the crystal structure of Peridinin–Chlorophyll–Protein, in particular, a peridinin–peridinin and a peridinin–chlorophyll-a dimer, and present quantum chemical evidence for excited states that exist beyond the confines of single peridinin and chlorophyll chromophores. These dark multichromophoric states, emanating from the intermolecular packing native to Peridinin–Chlorophyll–Protein, include a correlated triplet pair comprising neighbouring peridinin excitations and a charge-transfer interaction between peridinin and the adjacent chlorophyll-a. Lastly, we surmise that such dark multichromophoric states may explain two spectral mysteries in light-harvesting pigments: the sub-200-fs singlet fission observed in carotenoid aggregates, and the sub-200-fs chlorophyll-a hole generation in Peridinin–Chlorophyll–Protein.
Taffet, Elliot J., et al. "Uncovering dark multichromophoric states in Peridinin–Chlorophyll–Protein." Journal of the Royal Society Interface, vol. 17, no. 164, Mar. 2020. https://doi.org/10.1098/rsif.2019.0736
Taffet, Elliot J., Fassioli, Francesca, Toa, Zi D., Beljonne, David, & Scholes, Gregory D. (2020). Uncovering dark multichromophoric states in Peridinin–Chlorophyll–Protein. Journal of the Royal Society Interface, 17(164). https://doi.org/10.1098/rsif.2019.0736
Taffet, Elliot J., Fassioli, Francesca, Toa, Zi D., et al., "Uncovering dark multichromophoric states in Peridinin–Chlorophyll–Protein," Journal of the Royal Society Interface 17, no. 164 (2020), https://doi.org/10.1098/rsif.2019.0736
@article{osti_1777899,
author = {Taffet, Elliot J. and Fassioli, Francesca and Toa, Zi D. and Beljonne, David and Scholes, Gregory D.},
title = {Uncovering dark multichromophoric states in Peridinin–Chlorophyll–Protein},
annote = {It has long been recognized that visible light harvesting in Peridinin–Chlorophyll–Protein is driven by the interplay between the bright (S2) and dark (S1) states of peridinin (carotenoid), along with the lowest-lying bright (Qy) and dark (Qx) states of chlorophyll-a. Here, we analyse a chromophore cluster in the crystal structure of Peridinin–Chlorophyll–Protein, in particular, a peridinin–peridinin and a peridinin–chlorophyll-a dimer, and present quantum chemical evidence for excited states that exist beyond the confines of single peridinin and chlorophyll chromophores. These dark multichromophoric states, emanating from the intermolecular packing native to Peridinin–Chlorophyll–Protein, include a correlated triplet pair comprising neighbouring peridinin excitations and a charge-transfer interaction between peridinin and the adjacent chlorophyll-a. Lastly, we surmise that such dark multichromophoric states may explain two spectral mysteries in light-harvesting pigments: the sub-200-fs singlet fission observed in carotenoid aggregates, and the sub-200-fs chlorophyll-a hole generation in Peridinin–Chlorophyll–Protein.},
doi = {10.1098/rsif.2019.0736},
url = {https://www.osti.gov/biblio/1777899},
journal = {Journal of the Royal Society Interface},
issn = {ISSN 1742-5689},
number = {164},
volume = {17},
place = {United States},
publisher = {The Royal Society},
year = {2020},
month = {03}}
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; European Union's H2020 Marie Skłodowska-Curie actions
Grant/Contract Number:
SC0019370
OSTI ID:
1777899
Journal Information:
Journal of the Royal Society Interface, Journal Name: Journal of the Royal Society Interface Journal Issue: 164 Vol. 17; ISSN 1742-5689