The dark side of energy transport along excitonic wires: On-site energy barriers facilitate efficient, vibrationally mediated transport through optically dark subspaces.

We present a novel, counter-intuitive method, based on dark-state protection, for significantly improving exciton transport efficiency through "wires" comprising a chain of molecular sites with an intrinsic energy gradient. Specifically, by introducing "barriers" to the energy landscape at regular intervals along the transport path, we find that undesirable radiative recombination processes are suppressed due to a clear separation of sub-radiant and super-radiant eigenstates in the system. This, in turn, can lead to an improvement in transmitted power by many orders of magnitude, even for very long chains. From there, we analyze the robustness of this phenomenon to changes in both system and environment properties to show that this effect can be beneficial over a range of different thermal and optical environment regimes. Finally, we show that the novel energy landscape presented here may provide a useful foundation for overcoming the short length scales over which exciton diffusion typically occurs in organic photo-voltaics and other nanoscale transport scenarios, thus leading to considerable potential improvements in the efficiency of such devices.

Photocell Optimization Using Dark State Protection.

Conventional photocells suffer a fundamental efficiency threshold imposed by the principle of detailed balance, reflecting the fact that good absorbers must necessarily also be fast emitters. This limitation can be overcome by "parking" the energy of an absorbed photon in a dark state which neither absorbs nor emits light. Here we argue that suitable dark states occur naturally as a consequence of the dipole-dipole interaction between two proximal optical dipoles for a wide range of realistic molecular dimers. We develop an intuitive model of a photocell comprising two light-absorbing molecules coupled to an idealized reaction center, showing asymmetric dimers are capable of providing a significant enhancement of light-to-current conversion under ambient conditions. We conclude by describing a road map for identifying suitable molecular dimers for demonstrating this effect by screening a very large set of possible candidate molecules.

When do perturbative approaches accurately capture the dynamics of complex quantum systems?

Understanding the dynamics of higher-dimensional quantum systems embedded in a complex environment remains a significant theoretical challenge. While several approaches yielding numerically converged solutions exist, these are computationally expensive and often provide only limited physical insight. Here we address the question: when do more intuitive and simpler-to-compute second-order perturbative approaches provide adequate accuracy? We develop a simple analytical criterion and verify its validity for the case of the much-studied FMO dynamics as well as the canonical spin-boson model.