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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

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:
 [1];  [2];  [1];  [1];  [3];  [4];  [5]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  2. Univ. of Saskatchewan, Saskatoon, SK (Canada). Dept. of Physics and Engineering Physics; Canadian Light Sources, Inc., Saskatoon, SK (Canada)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Hacettepe Univ., Ankara (Turkey)
  4. DESY Photon Science, Hamburg (Germany)
  5. 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:
Journal Article: 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. 2016. "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},
url = {https://www.osti.gov/biblio/1321438}, journal = {Scientific Reports},
issn = {2045-2322},
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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Works referencing / citing this record:

Discovering Hidden Material Properties of MgCl 2 at Atomic Resolution with Structured Temporal Electron Illumination of Picosecond Time Resolution
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