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Title: Phosphorus Dimerization in Gallium Phosphide at High Pressure

Abstract

Using combined experimental and computational approaches, we show in this paper 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.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [3];  [1];  [1];  [4];  [2]
  1. Univ. of Nevada, Las Vegas, NV (United States)
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  4. Carnegie Inst. of Washington, Argonne, IL (United States). Geophysical Lab., High Pressure Collaborative Access Team (HPCAT)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); National Aeronautic and Space Administration (NASA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; National Science Foundation (NSF)
OSTI Identifier:
1469659
Alternate Identifier(s):
OSTI ID: 1581485
Report Number(s):
SAND2017-7495J; LLNL-JRNL-699313
Journal ID: ISSN 0020-1669; 655398
Grant/Contract Number:  
AC04-94AL85000; AC52-07NA27344; NA0001982; NNX10AN23H; NA0003525; NA0001974; FG02-99ER45775; AC02−06CH11357; EAR 11- 57758; EAR-1128799; FG02-94ER14466
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 5; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

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. https://www.osti.gov/servlets/purl/1469659.
@article{osti_1469659,
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 in this paper 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.},
doi = {10.1021/acs.inorgchem.7b02478},
journal = {Inorganic Chemistry},
number = 5,
volume = 57,
place = {United States},
year = {2018},
month = {2}
}

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Figures / Tables:

Table 1 Table 1: Structural parameters of GaP-$oS$24.

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.