Phosphorus Dimerization In Gallium Phosphide At High Pressure

Authors

B Lavina, University of Nevada, Las VegasFollow
E Kim, University of Nevada, Las VegasFollow
H CynnFollow
P F. WeckFollow
K Seaborg, University of Nevada, Las VegasFollow
E Siska, University of Nevada, Las VegasFollow
Y Meng, Carnegie Institution of WashingtonFollow
W Evans, Lawrence Livermore National LaboratoryFollow

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

Repository Citation

Lavina, B., Kim, E., Cynn, H., Weck, P. F., Seaborg, K., Siska, E., Meng, Y., Evans, W. (2018). Phosphorus Dimerization In Gallium Phosphide At High Pressure. Inorganic Chemistry, 57(5), 2432-2437. American Chemical Society.
http://dx.doi.org/10.1021/acs.inorgchem.7b02478