Impact of inhomogeneities on optical and transport properties of molecular aggregates

The goal of my Ph.D. research is to investigate how structural features of objects which are composed of few thousand molecules, called molecular aggregates, affect their properties. This research has both fundamental relevance and technological applications. Fundamentally, the molecular aggregates are of just the right size to observe both quantum mechanical effects (because they are small enough) and collective effects (because they are large enough). This combination leads to their novel exotic properties which can be employed for various applications. One of their most interesting applications is as light-harvesting complexes in natural photosynthetic systems. For instance, green sulfur photosynthetic bacteria which are found at depths of 100 m in the Black Sea survive the scarce light condition by employing tubular molecular aggregates. These tubular molecular aggregates can absorb sunlight and transfer the absorbed energy with extremely high efficiency, such that almost all absorbed energy is delivered to the part where it is converted to chemical energy. This has inspired the synthesis of artificial mimics for application in artificial photosynthesis and photovoltaic applications. To accomplish such applications, we must understand how disorder or inhomogeneity in the structure, which is inevitable during their synthesis, impacts their properties and resulting functions. From our research, we learned how inhomogeneity in the orientation of the molecules and size of the molecular aggregates influence optical properties, as well as, how disorder in the energy of individual molecules impact the transfer of excitation energy. These insights contribute to realizing the light-harvesting applications of these molecular aggregates

Simulating Fluorescence-Detected Two-Dimensional Electronic Spectroscopy of Multichromophoric Systems

We present a theory for modeling fluorescence-detected two-dimensional electronic spectroscopy of multichromophoric systems. The theory is tested by comparison of the predicted spectra of the light-harvesting complex LH2 with experimental data. A qualitative explanation of the strong cross-peaks as compared to conventional two-dimensional electronic spectra is given. The strong cross-peaks are attributed to the clean ground-state signal that is revealed when the annihilation of exciton pairs created on the same LH2 complex cancels oppositely signed signals from the doubly excited state. This annihilation process occurs much faster than the nonradiative relaxation. Furthermore, the line shape difference is attributed to slow dynamics, exciton delocalization within the bands, and intraband exciton-exciton annihilation. This is in line with existing theories presented for model systems. We further propose the use of time-resolved fluorescence-detected two-dimensional spectroscopy to study state-resolved exciton-exciton annihilation

Interplay between structural hierarchy and exciton diffusion in artificial light harvesting

Unravelling the nature of energy transport in multi-chromophoric photosynthetic complexes is essential to extract valuable design blueprints for light-harvesting applications. Long-range exciton transport in such systems is facilitated by a combination of delocalized excitation wavefunctions (excitons) and remarkable exciton diffusivities. The unambiguous identification of the exciton transport, however, is intrinsically challenging due to the system's sheer complexity. Here we address this challenge by employing a novel spectroscopic lab-on-a-chip approach: A combination of ultrafast coherent two-dimensional spectroscopy and microfluidics working in tandem with theoretical modelling. This allowed us to unveil exciton transport throughout the entire hierarchical supramolecular structure of a double-walled artificial light-harvesting complex. We show that at low exciton densities, the outer layer acts as an antenna that supplies excitons to the inner tube, while under high excitation fluences it protects the inner tube from overburning. Our findings shed light on the excitonic trajectories across different sub-units of a multi-layered supramolecular structure and underpin the great potential of artificial light-harvesting complexes for directional excitation energy transport.Comment: Submitted to Nature Communications; main manuscript 37 pages (incl. references) and 5 figures. SI 59 pages (incl. references) and 25 Figure

Ultrathin molecule-based magnetic conductors: A step towards flexible electronics

Organic-inorganic hybrid materials have shown a remarkable and rapid development during the past decade because they can be tailored to obtain new device concepts with controlled physical properties. Here, we report on the electronic and magnetic properties of multilayer organic-inorganic hybrid films. Electrical transport properties arising from the pi electrons in the organic layer are characteristic of a metallic state at high temperature and evolve into a state described by two-dimensional variable range hopping when temperature decreases below 150 K. The intrinsic electronic behavior of the hybrid films was further studied via the optical properties in the IR range. The optical response confirms the metallic character of the hybrid films. In the second part, the magnetic properties are discussed. A long-range ferromagnetic order with an ordering temperature of similar to 1 K is revealed in the Gd-based hybrid film. The Cu-based hybrid film, however, shows more extended ferromagnetic exchange interactions than the Gd-based hybrid LB film

Structural Variations in Chlorosomes from Wild-Type and a bchQR Mutant of Chlorobaculum tepidum Revealed by Single-Molecule Spectroscopy

Green sulfur bacteria can grow photosynthetically by absorbing only a few photons per bacteriochlorophyll molecule per day. They contain chlorosomes, perhaps the most efficient light-harvesting antenna system found in photosynthetic organisms. Chlorosomes contain supramolecular structures comprising hundreds of thousands of bacteriochlorophyll molecules, which are properly positioned with respect to one another solely by self-assembly and not by using a protein scaffold as a template for directing the mutual arrangement of the monomers. These two featureshigh efficiency and self-assemblyhave attracted considerable attention for developing light-harvesting systems for artificial photosynthesis. However, reflecting the heterogeneity of the natural system, detailed structural information at atomic resolution of the molecular aggregates is not yet available. Here, we compare the results for chlorosomes from the wild type and two mutants of Chlorobaculum tepidum obtained by polarization-resolved, single-particle fluorescence-excitation spectroscopy and theoretical modeling with results previously obtained from nuclear-magnetic resonance spectroscopy and cryo-electron microscopy. Only the combination of information obtained from all of these techniques allows for an unambiguous description of the molecular packing of bacteriochlorophylls within chlorosomes. In contrast to some suggestions in the literature, we find that, for the chlorosomes from the wild type as well as for those from mutants, the dominant secondary structural element features tubular symmetry following a very similar construction principle. Moreover, the results suggest that the various options for methylation of the bacteriochlorophyll molecules, which are a primary source of the structural (and spectral) heterogeneity of wild-type chlorosome samples, are exploited by nature to achieve improved spectral coverage at the level of individual chlorosomes