Anisotropic Structural Collapse of Mg3Sb2 and Mg3Bi2 at High PressureClick to copy article linkArticle link copied!
- Mario Calderón-CuevaMario Calderón-CuevaChemical Engineering and Materials Science Department, Michigan State University, East Lansing, Michigan 48824, United StatesMore by Mario Calderón-Cueva
- Wanyue PengWanyue PengChemical Engineering and Materials Science Department, Michigan State University, East Lansing, Michigan 48824, United StatesMore by Wanyue Peng
- Samantha M. ClarkeSamantha M. ClarkeLawrence Livermore National Laboratory, 7000 East Avenue, Livermore, California 94550, United StatesMore by Samantha M. Clarke
- Jingxuan DingJingxuan DingDepartment of Mechanical Engineering and Materials Science, Duke University, Durham, North Carolina 27708, United StatesMore by Jingxuan Ding
- Benjamin L. BrugmanBenjamin L. BrugmanDepartment of Earth and Environmental Sciences, Michigan State University, East Lansing, Michigan 48824, United StatesMore by Benjamin L. Brugman
- Gill LeventalGill LeventalChemical Engineering and Materials Science Department, Michigan State University, East Lansing, Michigan 48824, United StatesMore by Gill Levental
- Ashiwini BalodhiAshiwini BalodhiChemical Engineering and Materials Science Department, Michigan State University, East Lansing, Michigan 48824, United StatesMore by Ashiwini Balodhi
- Megan RylkoMegan RylkoChemical Engineering and Materials Science Department, Michigan State University, East Lansing, Michigan 48824, United StatesMore by Megan Rylko
- Olivier DelaireOlivier DelaireDepartment of Mechanical Engineering and Materials Science, Duke University, Durham, North Carolina 27708, United StatesMore by Olivier Delaire
- James P. S. WalshJames P. S. WalshDepartment of Chemistry, University of Massachusetts Amherst, Amherst, Massachusetts 01003, United StatesMore by James P. S. Walsh
- Susannah M. DorfmanSusannah M. DorfmanDepartment of Earth and Environmental Sciences, Michigan State University, East Lansing, Michigan 48824, United StatesMore by Susannah M. Dorfman
- Alexandra Zevalkink*Alexandra Zevalkink*Email: [email protected]Chemical Engineering and Materials Science Department, Michigan State University, East Lansing, Michigan 48824, United StatesMore by Alexandra Zevalkink
Abstract

Alloys between Mg3Sb2 and Mg3Bi2 have recently been shown to be exceptional thermoelectric materials due in part to their anomalously low thermal conductivity. In the present study, in situ high-pressure synchrotron X-ray diffraction was used to investigate the structure and bonding in Mg3Sb2 and Mg3Bi2 at pressures up to 50 GPa. Our results confirm prior predictions of isotropic in-plane and out-of-plane compressibility but reveal large disparities between the bond strength of the two distinct Mg sites. Using single-crystal diffraction, we show that the octahedral Mg–Sb bonds are significantly more compressible than the tetrahedral Mg–Sb bonds in Mg3Sb2, which lends support to prior arguments that the weaker octahedral Mg bonds are responsible for the anomalous thermal properties of Mg3Sb2 and Mg3Bi2. Further, we report the discovery of a displacive and reversible phase transition in both Mg3Sb2 and Mg3Bi2 above 7.8 and 4.0 GPa, respectively. The transition to the high-pressure structure involves a highly anisotropic volume collapse, in which the out-of-plane axis compresses significantly more than the in-plane axes. Single-crystal diffraction at high pressure was used to solve the monoclinic high-pressure structure (C2/m), which is a distorted variant of the ambient-pressure structure containing four unique Mg coordination environments.
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