title: Electronic coherence lineshapes reveal hidden excitonic correlations in photosynthetic light harvesting.
abstract: The effective absorption cross-section of a molecule (acceptor) can be greatly increased by associating it with a cluster of molecules that absorb light and transfer the excitation energy to the acceptor molecule. The basic mechanism of such light harvesting by Förster resonance energy transfer (FRET) is well established, but recent experiments have revealed a new feature whereby excitation is coherently shared among donor and acceptor molecules during FRET. In the present study, two-dimensional electronic spectroscopy was used to examine energy transfer at ambient temperature in a naturally occurring light-harvesting protein (PE545 of the marine cryptophyte alga Rhodomonas sp. strain CS24). Quantum beating was observed across a range of excitation frequencies. The shapes of those features in the two-dimensional spectra were examined. Through simulations, we show that two-dimensional electronic spectroscopy provides a probe of the adiabaticity of the free energy landscape underlying light harvesting.
authors.affiliation: Department of Chemistry, Institute for Optical Sciences and Centre for Quantum Information and Quantum Control, University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 3H6 Canada.
authors.forename: Cathy Y
authors.initials: CY
authors.lastname: Wong
authors.forename: Richard M
authors.initials: RM
authors.lastname: Alvey
authors.forename: Daniel B
authors.initials: DB
authors.lastname: Turner
authors.forename: Krystyna E
authors.initials: KE
authors.lastname: Wilk
authors.forename: Donald A
authors.initials: DA
authors.lastname: Bryant
authors.forename: Paul M G
authors.initials: PM
authors.lastname: Curmi
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Silbey
authors.forename: Gregory D
authors.initials: GD
authors.lastname: Scholes
mesh_terms: D004735:Energy Transfer; D031541:Fluorescence Resonance Energy Transfer; D045342:Light-Harvesting Protein Complexes / Q000528:radiation effects*; D010788:Photosynthesis; D013057:Spectrum Analysis / Q000379:methods
chemical_list: D045342:Light-Harvesting Protein Complexes