Modeling the polymorphism of pentacene

Abstract

Thin films of pentacene are known to crystallize in at least four different polymorphs. All polymorphs are layered structures that are characterized by their interlayer spacing d(001). We develop a model that rationalizes the size of the interlayer spacing in terms of intralayer shifts of the pentacene molecules along their long molecular axes. It explains the wide variety of interlayer spacings, without distorting the herringbone pattern that is characteristic of many acenes. Using two simple theoretical models, we attempt to relate the intralayer shifts with the dominant, although weak, interatomic interactions (van der Waals, weak electrostatic, and covalent). For two polymorphs, a consistent picture is found. A full understanding of the other two, substrate-induced, polymorphs probably requires consideration of interlayer interactions