An analytical continuation approach for evaluating emission lineshapes of molecular aggregates and the adequacy of multichromophoric Förster theory

In large photosynthetic chromophore-protein complexes not all chromophores are coupled strongly, and thus the situation is well described by formation of delocalized states in certain domains of strongly coupled chromophores. In order to describe excitation energy transfer among different domains without performing extensive numerical calculations,one of the most popular techniques is a generalization of Forster theory to multichromophoric aggregates (generalized Forster theory) proposed by Sumi [J.Phys.Chem.B,103,252(1999)] and Scholes and Fleming [J.Phys.Chem.B 104,1854(2000)]. The aim of this paper is twofold. In the first place, by means of analytic continuation and a time convolutionless quantum master equation approach, a theory of emission lineshape of multichromophoric systems or molecular aggregates is proposed. In the second place,a comprehensive framework that allows for a clear,compact and effective study of the multichromophoric approach in the full general version proposed by Jang, Newton and Silbey [Phys. Rev. Lett.,92,218301,(2004)] is developed. We apply the present theory to simple paradigmatic systems and we show: the effectiveness of time-convolutionless techniques in deriving lineshape operators; how the multichromophoric approach can give significant improvements in the determination of energy transfer rates in particular when the systems under study are not the purely Forster regime. The presented scheme allows for an effective implementation of the multichromophoric Forster approach which may be of use for simulating energy transfer dynamics in large photosynthetic aggregates, for which massive computational resources are usually required. Furthermore,our method allows for a systematic comparison of multichromophoric Foster and generalized Forster theories and for a clear understanding of their respective limits of validity