High-pressure polymorphs of LiPN₂: A first-principles study

Abstract

In this work, high-pressure phase behavior of LiPN₂ within 0–300 GPa was studied by using an unbiased structure searching method in combination with first-principles calculations. Three pressureinduced phase transitions were predicted, as tI16→hR4→cF64→oP8 at 44, 136, and 259 GPa, respectively. The six-fold coordination environments were found for all high-pressure polymorphs, which are substantially different from the four-fold coordination environments observed in the tI16 structure. The hR4 and cF64 structures consist of close-packed PN₆ and LiN₆ octahedra connected by edge-sharing, whereas the oP8 structure is built up from edge- and face-sharing PN₆ and LiN₆ octahedra with N lying in the center of the trigonal prisms. The electronic structure analysis reveals that LiPN₂ is a semiconductor within the pressure range studied and P-N and Li-N bonds are covalent and ionic, respectively. The results obtained are expected to provide insight and guidance for future experiments on LiPN₂ and other alkali metal nitridophosphates.

Keywords

lithium nitridophosphates / phase transition / high pressure / first principles

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