Title

Phosphorus Dimerization In Gallium Phosphide At High Pressure

Document Type

Article

Publication Date

1-1-2018

Publication Title

Inorganic Chemistry

Publisher

American Chemical Society

Volume

57

Issue

5

First page number:

2432

Last page number:

2437

Abstract

Using combined experimental and computational approaches, we show that at 43 GPa and 1300 K gallium phosphide adopts the super-Cmcm structure, here indicated with its Pearson notation oS24. First-principles enthalpy calculations demonstrate that this structure is more thermodynamically stable above ∼20 GPa than previously proposed polymorphs. In contrast to other polymorphs, the oS24 phase shows a strong bonding differentiation and distorted fivefold coordination geometries of both P atoms. The shortest bond of the phase is a single covalent P-P bond measuring 2.171(11) Å at synthesis pressure. Phosphorus dimerization in GaP sheds light on the nature of the super-Cmcm phase and provides critical new insights into the high-pressure polymorphism of octet semiconductors. Bond directionality and anisotropy explain the relatively low symmetry of this high-pressure phase. © 2018 American Chemical Society.

Language

English

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