skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Phosphorus Dimerization in Gallium Phosphide at High Pressure

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. Here, 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.

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [4];  [1];  [5];  [6];  [3]
  1. High Pressure Science and Engineering Center, University of Nevada, Las Vegas, Nevada 89154, United States; Department of Physics and Astronomy, University of Nevada, Las Vegas, Nevada 89154, United States
  2. Department of Physics and Astronomy, University of Nevada, Las Vegas, Nevada 89154, United States
  3. Lawrence Livermore National Laboratory, Livermore, California 94550, United States
  4. Sandia National Laboratories, Albuquerque, New Mexico 87185, United States
  5. High Pressure Science and Engineering Center, University of Nevada, Las Vegas, Nevada 89154, United States
  6. HPCAT, Carnegie Institution of Washington, Argonne, Illinois 60439, United States
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); National Aeronautic and Space Administration (NASA)
OSTI Identifier:
1429807
Report Number(s):
SAND-2017-7495J
Journal ID: ISSN 0020-1669; 655398
DOE Contract Number:
AC04-94AL85000
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 57; Journal Issue: 5
Country of Publication:
United States
Language:
English

Citation Formats

Lavina, Barbara, Kim, Eunja, Cynn, Hyunchae, Weck, Philippe F., Seaborg, Kelly, Siska, Emily, Meng, Yue, and Evans, William. Phosphorus Dimerization in Gallium Phosphide at High Pressure. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.7b02478.
Lavina, Barbara, Kim, Eunja, Cynn, Hyunchae, Weck, Philippe F., Seaborg, Kelly, Siska, Emily, Meng, Yue, & Evans, William. Phosphorus Dimerization in Gallium Phosphide at High Pressure. United States. doi:10.1021/acs.inorgchem.7b02478.
Lavina, Barbara, Kim, Eunja, Cynn, Hyunchae, Weck, Philippe F., Seaborg, Kelly, Siska, Emily, Meng, Yue, and Evans, William. Fri . "Phosphorus Dimerization in Gallium Phosphide at High Pressure". United States. doi:10.1021/acs.inorgchem.7b02478.
@article{osti_1429807,
title = {Phosphorus Dimerization in Gallium Phosphide at High Pressure},
author = {Lavina, Barbara and Kim, Eunja and Cynn, Hyunchae and Weck, Philippe F. and Seaborg, Kelly and Siska, Emily and Meng, Yue and Evans, William},
abstractNote = {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. Here, 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.},
doi = {10.1021/acs.inorgchem.7b02478},
journal = {Inorganic Chemistry},
number = 5,
volume = 57,
place = {United States},
year = {Fri Feb 09 00:00:00 EST 2018},
month = {Fri Feb 09 00:00:00 EST 2018}
}