TY - GEN A1 - Bachhuber, Frederik A1 - Appen, Jörg von A1 - Dronskowski, Richard A1 - Schmidt, Peer A1 - Nilges, Tom A1 - Pfitzner, Arno A1 - Weihrich, Richard T1 - Van der Waals interactions in selected allotropes of phosphorus T2 - Zeitschrift für Kristallografie N2 - Selected allotropes of phosphorus are investigated by different levels of density functional theory (DFT) calculations to evaluate the relative stability orders with a special focus on the role of van der Waals interactions.Phosphorus is an excellent reference system with a large number of allotropes. Starting from low-dimensional molecular (0D, white P) and polymer structures (1D, P nanorods) to layered (2D, black P) and tubular structures (2D and 3D, crystalline forms of red P), covalent structure motifs are interconnected by van der Waals interactions. They are a key factor for the correct energetic description of all P allotropes. A comparative study is carried out within the local density approximation (LDA) and the generalized gradient approximation (GGA), with and without implementation of a dispersion correction by Grimme (GGA-D2). Our intention is to achieve a reasonable agreement of our calculations with experimental data, the plausibility of energy values, and the treatment of long-range interactions. The effect of van der Waals interactions is exemplified for the interlayer distances of black phosphorous and its electronic structure. KW - allotropes KW - band structure KW - DFT KW - phosphorous KW - stability KW - van der Waals Y1 - 2015 U6 - https://doi.org/10.1515/zkri-2014-1800 SN - 2196-7105 VL - 230 IS - 2 SP - 107 EP - 115 ER - TY - GEN A1 - Bachhuber, Frederik A1 - Appen, Jörg von A1 - Dronskowski, Richard A1 - Schmidt, Peer A1 - Nilges, Tom A1 - Pfitzner, Arno A1 - Weihrich, Richard T1 - The Extended Stability Range of Phosphorus Allotropes T2 - Angewandte Chemie / International edition N2 - 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 [P12] nanorods and not-yet-isolated [P14] 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. KW - density functional calculations KW - phosphorus KW - structure elucidation KW - van der Waals interactions Y1 - 2014 UR - http://onlinelibrary.wiley.com/doi/10.1002/anie.201404147/full U6 - https://doi.org/10.1002/anie.201404147 SN - 1521-3773 VL - 53 IS - 43 SP - 11629 EP - 11633 ER -