Long-range embedding of molecular ions and excitations in a polarizable molecular environment

C. Poelking, D. Andrienko, J. Chem. Theory Comput. , 2016 [doi]

We present a perturbative treatment of localized aperiodic excitations (charge charge transfer and excitonic states) interacting with a periodic molecular environment. The method rigorously accounts for the long-ranged interaction of charges with a net-quadrupolar background with the conditional convergence of the interaction sum removed by bulk or thin-film shape corrections. We illustrate how long-range interactions qualitatively and quantitatively impact the densities of states and level profiles in heterostructures of organic semiconductors investigating the role of molecular architecture packing and orientation. In accounting for mesoscale fields we obtain the energetics of charge carriers in both crystalline and mesoscopically amorphous systems with high accuracy.