In a larger picture of charge separation processes in OPV, the initial polaron-pair formation on a single polymer/molecule would favor subsequent charge separation within polymer aggregates or at the donor/acceptor interface. The concept of interpreting the dipole moment and CAE as indicators for electron and hole wavefunction splitting or recombination, respectively, can also be applied to the aggregates and the interface itself, making this approach useful for the study and qualitative analysis of various polymer structures as well as complex morphology effects. The latter are known to have a strong influence on the dissociation of excitons through a disordered energy landscape, close packing for extended delocalization of excitonic states and thus an extended dipole moment, and relative orientation to influence the interfacial CT states. However, the theoretical description and effects of large ensembles of different aggregates/interfaces is limited in the literature. Thus, modeling different aggregate ensembles of donor-acceptor interfaces, e.g., the widely used and promising polymer PM6 and the non-fullerene acceptor Y6, and analyzing their static or dynamic CAE as well as dipole moment can provide clues to advantages of certain aggregates and possible charge separation pathways.