The Extended Stability Range of Phosphorus Allotropes

Abstract

Phosphorus displays fascinating structural diversity and the discovery of new modifications continues to attract attention. In this work, a complete stability range of known and novel crystalline allotropes of phosphorus is described for the first time. This includes recently discovered tubular modifications and the prediction of not‐yet‐known crystal structures of [P 12] nanorods and not‐yet‐isolated [P 14] nanorods. Despite significant structural differences, all P allotropes consist of covalent substructures, which are held together by van der Waals interactions. Their correct reproduction by ab initio calculations is a core issue of current research. While some predictions with the established DFT functionals GGA and LDA differ significantly from experimental data in the description of the P allotropes, consistently excellent agreement with the GGA‐D2 approach is used to predict the solid structures of the P nanorods.