Journal of Physical Chemistry B, Vol.108, No.3, 1085-1095, 2004
Excitation energy transfer in model light-harvesting antennae
Applications of light-harvesting arrays range from alternative sources of energy to the field of photonic and optoelectronic devices. Antenna arrays can absorb and transfer light energy to do electrochemical work. Photosynthetic light-harvesting units that are found in nature exhibit highly efficient utilization of solar energy. Recently, biomimetic arrays have successfully been designed. Several questions pertaining to light harvesting arrays still need to be addressed and studied fully. For example, do various antenna geometries give rise to radically different excitation energy transfer, and are the structures in nature especially well-suited for energy transfer? If not, how should specific monomeric structures be arranged to optimize light harvesting? This paper simulates the energy transfer dynamics in several model systems based on monomeric units of the photosynthetic light-harvesting complex, LH2, of purple bacteria using the Haken-Strobl parametrization of the Stochastic Liouville equation. It is found that the coherence size is strongly dependent on the magnitude of the stochastic bath fluctuations and the model geometry. Although static disorder is found to alter the coherence sizes, the overall trends observed in models of increasing ring size do not depend on its absence. A comparison of linear and circular arrays shows that the exciton dynamics has very different scaling properties as a function of array size for the periodic boundary conditions found in ring antenna systems. By monitoring coherence sizes, it is shown that model systems of heterodimers, monomers and homodimers in ring structures exhibit similar energy transfer characteristics. It is also shown that the short-time excitation energy dynamics in coupled ring systems depends on the initial excitation process.