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Compressed MgCl2 Reveals Multiple Pathways to Cotunnite Structures.

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High pressure transforms magnesium dichloride (MgCl2) into new structures, revealing trigonal prismatic coordination and complex layered-to-framework transitions. These findings advance materials science and high-pressure chemistry.

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Area of Science:

  • Materials Science
  • High-Pressure Chemistry
  • Mineral Physics

Background:

  • MeX2 compounds are crucial for understanding materials under extreme conditions.
  • High pressure induces phase transitions in these materials, altering their structure and properties.

Purpose of the Study:

  • To investigate the high-pressure phase transitions of magnesium dichloride (MgCl2).
  • To identify new structural polymorphs and coordination geometries in MgCl2 under compression.
  • To elucidate the transformation pathways of MeX2 compounds towards cotunnite-type structures.

Main Methods:

  • Synthesis of anhydrous MgCl2 using direct reaction in laser-heated diamond anvil cells.
  • High-pressure experiments conducted from 7 to 83 GPa.
  • Single-crystal X-ray diffraction for structural identification.
  • Ab initio calculations for stability, equations of state, and electronic properties.

Main Results:

  • Observed the first trigonal prismatic coordination in MeX2 compounds, specifically in MgCl2.
  • Identified two new high-pressure phases of MgCl2: orthorhombic oP72 and cotunnite-type oP12.
  • Documented a pressure-induced structural transition from layered (hP3) to 3D frameworks (oP72 and oP12).
  • Experimental data aligned well with theoretical ab initio calculations.

Conclusions:

  • The study reveals complex structural evolution in MgCl2 under high pressure.
  • New polymorphs and coordination behaviors were discovered, expanding knowledge of MeX2 phase transitions.
  • The findings provide insights into transformation pathways relevant to materials science and high-pressure chemistry.