Quantum Resources for Efficient Excitation Energy Transfer in Natural and Artificial Pigment-Protein Molecular Aggregates

University dissertation from Uppsala : Acta Universitatis Upsaliensis

Abstract: Recently, long-lasting quantum effects in a number of photosynthetic complexes, which are pigment-protein molecular aggregates (PPMAs), were experimentally verified. These findings created an interest in trying to connect the known highly efficient excitation energy transfer (EET) in these systems to the existence of quantum effects such as quantum coherence and quantum correlations. It also raised the question of how these sensitive quantum effects can survive in such a macroscopic system.This thesis explores the existence and possible role of quantum effects in the EET in PPMAs. These systems can be modeled as non-Markovian open quantum systems and quantum effects can be investigated and quantified by methods developed in quantum information theory.Firstly, it is found that quantum nonlocal correlations in the EET in the Fenna-Matthews-Olson complex - a PPMA found in nature - are unlikely to exist when the initial excitation occurs in a natural manner. When the initial excitation occurs in an artificial manner by localization of the excitation on one pigment, nonlocal correlations exist on a short time scale. It is further found that in order for nonlocal correlations to be preserved in such a system, the excitation must be trapped on two pigments at the time and these pigments must not interact strongly with other pigments in the complex.Secondly, it is shown that quantum coherence is not in general a resource for efficient EET in model systems consisting of a network of pigments; systems optimized with respect to the amount of coherence do not coincide with systems with optimal EET efficiency between two end-site pigments.Thirdly, it is found that environmental effects and system-environment interactions can be tuned to optimize the EET efficiency in model PPMAs. The features of optimal environments highly depends on the structure of the pigment system and in particular, the relationship between the pigments excitation energies. It is further shown that a non-Markovian dynamics cannot be connected to an increased EET efficiency in these systems.