High-pressure X-ray diffraction, Raman, and computational studies of MgCl2 up to 1 Mbar: Extensive pressure stability of the β-MgCl2 layered structure

Stavrou, Elissaios; Yao, Yansun; Zaug, Joseph M.; Bastea, Sorin; Kalkan, Bora; Konôpková, Zuzana; Kunz, Martin

doi:10.1038/srep30631

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

Journal Article · Fri Aug 12 00:00:00 EDT 2016 · Scientific Reports

DOI:https://doi.org/10.1038/srep30631· OSTI ID:1321438

Stavrou, Elissaios ^[1]; Yao, Yansun ^[2]; Zaug, Joseph M. ^[1]; Bastea, Sorin ^[1]; Kalkan, Bora ^[3]; Konôpková, Zuzana ^[4]; Kunz, Martin ^[5]

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)

© 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.

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Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC52-07NA27344; HDTRA1-11-1-4538I; AC02-05CH11231

OSTI ID:: 1321438

Alternate ID(s):: OSTI ID: 1379564

Report Number(s):: LLNL-JRNL-688100

Journal Information:: Scientific Reports, Vol. 6; ISSN 2045-2322

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 10 works

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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