LAUSR

The morphology of layered aggregates of N,N′-ditridecylperylene-3,4,9,10-tetracarboxylic diimide (PTCDI-C13), a prototypical n-type semiconductor for organic electronic devices, was investigated by molecular dynamics and corroborated by metadynamics simulations. Calculations were targeted to ordered 3D aggregates, differing in the relative orientation of the perylene π-cores and on the degree of interdigitation among contiguous planar layers. Our simulations indicated the noninterdigitated cofacial structure as the thermodynamically most stable form of ordered PTCDI-C13 aggregates, in both bulk crystals and bilayers. Other structures, however, may occur in the growth of PTCDI-C13 under kinetic conditions. Density functional theory calculations were also performed to evaluate the relative total electronic energy of 3D crystals of PTCDI-C13 and related transfer integrals, correlating structure with potential charge-transport properties in devices. The most stable ordered aggregated form of PTCDI-C13 exhibit...