title: A stochastic reorganizational bath model for electronic energy transfer.
abstract: Environmentally induced fluctuations of the optical gap play a crucial role in electronic energy transfer dynamics. One of the simplest approaches to incorporate such fluctuations in energy transfer dynamics is the well known Haken-Strobl-Reineker (HSR) model, in which the energy-gap fluctuation is approximated as white noise. Recently, several groups have employed molecular dynamics simulations and excited-state calculations in conjunction to account for excitation energies' thermal fluctuations. On the other hand, since the original work of HSR, many groups have employed stochastic models to simulate the same transfer dynamics. Here, we discuss a rigorous connection between the stochastic and the atomistic bath models. If the phonon bath is treated classically, time evolution of the exciton-phonon system can be described by Ehrenfest dynamics. To establish the relationship between the stochastic and atomistic bath models, we employ a projection operator technique to derive the generalized Langevin equations for the energy-gap fluctuations. The stochastic bath model can be obtained as an approximation of the atomistic Ehrenfest equations via the generalized Langevin approach. Based on this connection, we propose a novel scheme to take account of reorganization effects within the framework of stochastic models. The proposed scheme provides a better description of the population dynamics especially in the regime of strong exciton-phonon coupling. Finally, we discuss the effect of the bath reorganization in the absorption and fluorescence spectra of ideal J-aggregates in terms of the Stokes shifts. We find a simple expression that relates the reorganization contribution to the Stokes shifts - the reorganization shift - to the ideal or non-ideal exciton delocalization in a J-aggregate. The reorganization shift can be described by three parameters: the monomer reorganization energy, the relaxation time of the optical gap, and the exciton delocalization length. This simple relationship allows one to understand the physical origin of the Stokes shifts in molecular aggregates.
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
authors.forename: Takatoshi
authors.initials: T
authors.lastname: Fujita
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
authors.forename: Joonsuk
authors.initials: J
authors.lastname: Huh
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
authors.forename: Alán
authors.initials: A
authors.lastname: Aspuru-Guzik
mesh_terms: D004583:Electrons; D004735:Energy Transfer; D045342:Light-Harvesting Protein Complexes / Q000737:chemistry*; D060739:Phonons; D011789:Quantum Theory; D013269:Stochastic Processes
chemical_list: D045342:Light-Harvesting Protein Complexes