Excitation transport in molecular aggregates with thermal motion

Abstract

Molecular aggregates can under certain conditions transport electronic excitation energy over large distances due to dipole–dipole interactions. Here, we explore to what extent thermal motion of entire monomers can guide or enhance this excitation transport. The motion induces changes of aggregate geometry and hence modifies exciton states. Under certain conditions, excitation energy can thus be transported by the aggregate adiabatically, following a certain exciton eigenstate. While such transport is always slower than direct migration through dipole–dipole interactions, we show that transport through motion can yield higher transport efficiencies in the presence of on-site energy disorder than the static counterpart. For this we consider two simple models of molecular motion: (i) longitudinal vibrations of the monomers along the aggregation direction within their inter-molecular binding potential and (ii) torsional motion of planar monomers in a plane orthogonal to the aggregation direction. The parameters and potential shapes used are relevant to dye-molecule aggregates. We employ a quantum-classical method, in which molecules move through simplified classical molecular dynamics, while the excitation transport is treated quantum mechanically using Schrödinger's equation. For both models we find parameter regimes in which the motion enhances excitation transport, however these are more realistic for the torsional scenario, due to the limited motional range in a typical Morse type inter-molecular potential. We finally show that the transport enhancement can be linked to adiabatic quantum dynamics. This transport enhancement through adiabatic motion appears a useful resource to combat exciton trapping by disorder.