Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford, Oxford, OX1 3QR, UK.
Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, Oxford, OX1 3QZ, UK.
Angew Chem Int Ed Engl. 2023 Jun 12;62(24):e202216658. doi: 10.1002/anie.202216658. Epub 2023 May 5.
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.
无定形红磷 (a-P) 是元素结构化学中仍未解决的难题之一。在这里，我们结合机器学习和密度泛函理论 (DFT) 方法，从第一性原理出发阐明了 a-P 的结构、稳定性和化学键合。我们表明，a-P 结构的能量存在于一系列略高于与其密切相关的磷纳米棒的能量范围内，并且 a-P 的稳定性与结构弛豫和中程有序的程度有关。因此，我们通过现在包括以前理解不佳的无定形相，完成了磷同素异形体的稳定范围[Angew. Chem. Int. Ed. 2014, 53, 11629]，并量化了磷所有主要相中共价和范德华相互作用。我们还研究了电子态密度，包括氢化 a-P 的电子态密度。除了目前的研究之外，我们的结构模型有望实现更广泛的第一性原理研究——例如，基于 a-P 的电池材料。
