Structure and Bonding in Amorphous Red Phosphorus** |
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| Authors: | Yuxing Zhou Prof Stephen R Elliott Prof Volker L Deringer |
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| Institution: | 1. Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford, Oxford, OX1 3QR UK;2. Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, Oxford, OX1 3QZ UK |
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| Abstract: | Amorphous red phosphorus (a-P) is one of the remaining puzzling cases in the structural chemistry of the elements. Here, we elucidate the structure, stability, and chemical bonding in a-P from first principles, combining machine-learning and density-functional theory (DFT) methods. We show that a-P structures exist with a range of energies slightly higher than those of phosphorus nanorods, to which they are closely related, and that the stability of a-P is linked to the degree of structural relaxation and medium-range order. We thus complete the stability range of phosphorus allotropes Angew. Chem. Int. Ed. 2014 , 53, 11629] by now including the previously poorly understood amorphous phase, and we quantify the covalent and van der Waals interactions in all main phases of phosphorus. We also study the electronic densities of states, including those of hydrogenated a-P. Beyond the present study, our structural models are expected to enable wider-ranging first-principles investigations—for example, of a-P-based battery materials. |
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| Keywords: | Allotropes of Phosphorus Amorphous Materials Electronic Structure Machine Learning Solid-State Structures |
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