Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) Approach to the Correlated Exciton-Vibrational Dynamics in the FMO Complex

Abstract: The coupled quantum dynamics of excitonic and vibrational degrees of freedom is investigated for high-dimensional models of the Fenna-Matthews-Olson (FMO) complex. This includes a seven and an eight-site model with 518 and 592 harmonic vibrational modes, respectively. The coupling between local electronic transitions and vibrations is described within the Huang-Rhys model using parameters that are obtained by discretization of an experimental spectral density. Different pathways of excitation energy flow are analyzed in terms of the reduced one-exciton density matrix, focussing on the role of vibrational and vibronic excitation. Distinct features due to both competing time scales of vibrational and exciton motion and vibronically-assisted transfer are observed. The question of the effect of initial state preparation is addressed by comparing the case of an instantaneous Franck-Condon excitation at a single site with that of a laser field excitation.