Uncovering Dark Multichromophoric States in Peridinin-Chlorophyll-Protein

Overview

Journal J R Soc Interface

Specialties Biology
Biomedical Engineering
Biophysics

Date 2020 Mar 19

PMID 32183641

Citations 3

Authors

Elliot J Taffet

Francesca Fassioli

Zi S D Toa

David Beljonne

Gregory D Scholes

Affiliations

Soon will be listed here.

Abstract

It has long been recognized that visible light harvesting in Peridinin-Chlorophyll-Protein is driven by the interplay between the bright (S) and dark (S) states of peridinin (carotenoid), along with the lowest-lying bright (Q) and dark (Q) states of chlorophyll-. Here, we analyse a chromophore cluster in the crystal structure of Peridinin-Chlorophyll-Protein, in particular, a peridinin-peridinin and a peridinin-chlorophyll- 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-. 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- hole generation in Peridinin-Chlorophyll-Protein.

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