High-pressure X-ray diffraction, Raman, and computational studies of MgCl2 up to 1 Mbar: Extensive pressure stability of the β-MgCl2 layered structure
Abstract
© 2016 The Author(s). Magnesium chloride (MgCl 2 ) with the rhombohedral layered CdCl 2 -type structure (α-MgCl 2 ) has been studied experimentally using synchrotron angle-dispersive powder x-ray diffraction and Raman spectroscopy using a diamond-anvil cell up to 100 GPa at room temperature and theoretically using first-principles density functional calculations. The results reveal a pressure-induced second-order structural phase transition to a hexagonal layered CdI 2 -type structure (β-MgCl 2 ) at 0.7 GPa: the stacking sequence of the Cl anions are altered resulting in a reduction of the c-axis length. Theoretical calculations confirm this phase transition sequence and the calculated transition pressure is in excellent agreement with the experiment. Lattice dynamics calculations also reproduce the experimental Raman spectra measured for the ambient and high-pressure phase. According to our experimental results MgCl 2 remains in a 2D layered phase up to 100 GPa and further, the 6-fold coordination of Mg cations is retained. Theoretical calculations of relative enthalpy suggest that this extensive pressure stability is due to a low enthalpy of the layered structure ruling out kinetic barrier effects. This observation is unusual, as it contradicts with the general structural behavior of highly compressed AB 2 compounds.
- Authors:
-
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Univ. of Saskatchewan, Saskatoon, SK (Canada). Dept. of Physics and Engineering Physics; Canadian Light Sources, Inc., Saskatoon, SK (Canada)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Hacettepe Univ., Ankara (Turkey)
- DESY Photon Science, Hamburg (Germany)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1321438
- Alternate Identifier(s):
- OSTI ID: 1379564
- Report Number(s):
- LLNL-JRNL-688100
Journal ID: ISSN 2045-2322
- Grant/Contract Number:
- AC52-07NA27344; HDTRA1-11-1-4538I; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Scientific Reports
- Additional Journal Information:
- Journal Volume: 6; Journal ID: ISSN 2045-2322
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY
Citation Formats
Stavrou, Elissaios, Yao, Yansun, Zaug, Joseph M., Bastea, Sorin, Kalkan, Bora, Konôpková, Zuzana, and Kunz, Martin. High-pressure X-ray diffraction, Raman, and computational studies of MgCl2 up to 1 Mbar: Extensive pressure stability of the β-MgCl2 layered structure. United States: N. p., 2016.
Web. doi:10.1038/srep30631.
Stavrou, Elissaios, Yao, Yansun, Zaug, Joseph M., Bastea, Sorin, Kalkan, Bora, Konôpková, Zuzana, & Kunz, Martin. High-pressure X-ray diffraction, Raman, and computational studies of MgCl2 up to 1 Mbar: Extensive pressure stability of the β-MgCl2 layered structure. United States. https://doi.org/10.1038/srep30631
Stavrou, Elissaios, Yao, Yansun, Zaug, Joseph M., Bastea, Sorin, Kalkan, Bora, Konôpková, Zuzana, and Kunz, Martin. Fri .
"High-pressure X-ray diffraction, Raman, and computational studies of MgCl2 up to 1 Mbar: Extensive pressure stability of the β-MgCl2 layered structure". United States. https://doi.org/10.1038/srep30631. https://www.osti.gov/servlets/purl/1321438.
@article{osti_1321438,
title = {High-pressure X-ray diffraction, Raman, and computational studies of MgCl2 up to 1 Mbar: Extensive pressure stability of the β-MgCl2 layered structure},
author = {Stavrou, Elissaios and Yao, Yansun and Zaug, Joseph M. and Bastea, Sorin and Kalkan, Bora and Konôpková, Zuzana and Kunz, Martin},
abstractNote = {© 2016 The Author(s). Magnesium chloride (MgCl 2 ) with the rhombohedral layered CdCl 2 -type structure (α-MgCl 2 ) has been studied experimentally using synchrotron angle-dispersive powder x-ray diffraction and Raman spectroscopy using a diamond-anvil cell up to 100 GPa at room temperature and theoretically using first-principles density functional calculations. The results reveal a pressure-induced second-order structural phase transition to a hexagonal layered CdI 2 -type structure (β-MgCl 2 ) at 0.7 GPa: the stacking sequence of the Cl anions are altered resulting in a reduction of the c-axis length. Theoretical calculations confirm this phase transition sequence and the calculated transition pressure is in excellent agreement with the experiment. Lattice dynamics calculations also reproduce the experimental Raman spectra measured for the ambient and high-pressure phase. According to our experimental results MgCl 2 remains in a 2D layered phase up to 100 GPa and further, the 6-fold coordination of Mg cations is retained. Theoretical calculations of relative enthalpy suggest that this extensive pressure stability is due to a low enthalpy of the layered structure ruling out kinetic barrier effects. This observation is unusual, as it contradicts with the general structural behavior of highly compressed AB 2 compounds.},
doi = {10.1038/srep30631},
journal = {Scientific Reports},
number = ,
volume = 6,
place = {United States},
year = {Fri Aug 12 00:00:00 EDT 2016},
month = {Fri Aug 12 00:00:00 EDT 2016}
}
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