Journal article
Microscopic origin of pressure-induced isosymmetric transitions in fluoromanganate cryolites
Physical review. B, v 90(9)
24 Sep 2014
Abstract
Using first-principles density functional theory calculations, we investigate the hydrostatic pressure-induced reorientation of the Mn-F Jahn-Teller bond axis in the fluoride cryolite Na3MnF6. We find that a first-order isosymmetric phase transition (IPT) occurs between crystallographically equivalent monoclinic structures at approximately 2.15 GPa, consistent with earlier experimental studies. Mode-crystallography analyses of the pressure-dependent structures in the vicinity of the transition reveal a clear evolution of the Jahn-Teller bond distortions in cooperation with an asymmetrical stretching of the equatorial fluorine atoms in the MnF6 octahedral units. We identify a significant (70%) change in the orbital occupancy of the e(g) manifold of the 3d(4) Mn(III) to be responsible for the transition, stabilizing one monoclinic P2(1)/n variant over the other. The orbital reconstruction as a driving force for the transition is confirmed by analogous calculations of isostructural 3d(0) Na3ScF6, which shows no evidence of an IPT up to 6.82 GPa.
Metrics
Details
- Title
- Microscopic origin of pressure-induced isosymmetric transitions in fluoromanganate cryolites
- Creators
- Nenian Charles - Drexel UniversityJames M. Rondinelli - Drexel University
- Publication Details
- Physical review. B, v 90(9)
- Publisher
- Amer Physical Soc
- Number of pages
- 9
- Grant note
- 52138-DNI10 / American Chemical Society Petroleum Research Fund; American Chemical Society DE-AC02-06CH11357 / U.S. DOE, Office of Basic Energy Sciences (BES); United States Department of Energy (DOE) OCI-1053575 / National Science Foundation Grant; National Science Foundation (NSF)
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Materials Science and Engineering
- Web of Science ID
- WOS:000342137700001
- Scopus ID
- 2-s2.0-84907452480
- Other Identifier
- 991019330616104721
InCites Highlights
Data related to this publication, from InCites Benchmarking & Analytics tool:
- Collaboration types
- Domestic collaboration
- Web of Science research areas
- Materials Science, Multidisciplinary
- Physics, Applied
- Physics, Condensed Matter