Periodic density functional theory calculations are here used to investigate polymorphism in poly(butylene-2,6-naphthalate) (PBN) and to understand the intra- and inter-molecular effects which are responsible for its behavior. Despite its similarity to poly(butylene terephthalate), the larger pi-electron conjugation promoted by the presence of naphtyl rings generates peculiar intramolecular effects and stronger interchain packing interactions which cause some differences between the two polymers. This is particularly evident by comparing the structural and spectroscopic data predicted for the alpha and beta crystals with respect to the respective one dimensional infinite chain models. Two different interpretations have been proposed in the previous literature to describe the structural transitions from the alpha to the beta polymorph of PBN upon mechanical deformation or thermal treatments: from one hand, the setting on of a transplanar conformation on the methylene chains has been proposed while, on the other hand, a larger coplanarity of the ester groups and the naphtyl rings has been suggested. Our calculations reveal that both these effects are present in beta-PBN and should be both taken into account to give an interpretation of the trends observed by IR spectroscopy and structural characterization. (C) 2014 Elsevier Ltd. All rights reserved.