title: Two-dimensional spectroscopy of a molecular dimer unveils the effects of vibronic coupling on exciton coherences.
abstract: The observation of persistent oscillatory signals in multidimensional spectra of protein-pigment complexes has spurred a debate on the role of coherence-assisted electronic energy transfer as a key operating principle in photosynthesis. Vibronic coupling has recently been proposed as an explanation for the long lifetime of the observed spectral beatings. However, photosynthetic systems are inherently complicated, and tractable studies on simple molecular compounds are needed to fully understand the underlying physics. In this work, we present measurements and calculations on a solvated molecular homodimer with clearly resolvable oscillations in the corresponding two-dimensional spectra. Through analysis of the various contributions to the nonlinear response, we succeed in isolating the signal due to inter-exciton coherence. We find that although calculations predict a prolongation of this coherence due to vibronic coupling, the combination of dynamic disorder and vibrational relaxation leads to a coherence decay on a timescale comparable to the electronic dephasing time.
authors.affiliation: Institute for Optical Sciences and Departments of Chemistry and Physics, University of Toronto, 80 St George Street, Toronto, Ontario M5S 3H6, Canada.
authors.forename: Alexei
authors.initials: A
authors.lastname: Halpin
authors.affiliation: Institute for Optical Sciences and Departments of Chemistry and Physics, University of Toronto, 80 St George Street, Toronto, Ontario M5S 3H6, Canada.
authors.forename: Philip J M
authors.initials: PJ
authors.lastname: Johnson
authors.affiliation: Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.
authors.forename: Roel
authors.initials: R
authors.lastname: Tempelaar
authors.affiliation: Department of Chemistry and Biochemistry, University of Regina, 3737 Wascana Parkway, Regina, Saskatchewan S4S 0A2, Canada.
authors.forename: R Scott
authors.initials: RS
authors.lastname: Murphy
authors.affiliation: Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.
authors.forename: Jasper
authors.initials: J
authors.lastname: Knoester
authors.affiliation: Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.
authors.forename: Thomas L C
authors.initials: TL
authors.lastname: Jansen
authors.affiliation: 1] Institute for Optical Sciences and Departments of Chemistry and Physics, University of Toronto, 80 St George Street, Toronto, Ontario M5S 3H6, Canada [2] Max Planck Institute for the Structure and Dynamics of Matter, Atomically Resolved Dynamics Division, Building 99 (CFEL), Luruper Chaussee 149, 22761 Hamburg, Germany.
authors.forename: R J Dwayne
authors.initials: RJ
authors.lastname: Miller
mesh_terms: D019281:Dimerization; D004583:Electrons; D004735:Energy Transfer; D045342:Light-Harvesting Protein Complexes / Q000737:chemistry*; D008958:Models, Molecular; D011108:Polymers / Q000737:chemistry; D013057:Spectrum Analysis / Q000379:methods*
chemical_list: D045342:Light-Harvesting Protein Complexes; D011108:Polymers