Journal article
Reconstructive Transitions from Rotations of Rigid Heteroanionic Polyhedra
Journal of the American Chemical Society, v 138(36), pp 11882-11889
14 Sep 2016
PMID: 27532822
Featured in Collection : UN Sustainable Development Goals @ Drexel
Abstract
Phase transitions are ubiquitous in structurally complex transition metal compounds, composed of homoanionic polyhedra, including nitrides, oxides, and fluorides. The symmetry breaking that occurs across polymorphic transitions is often achieved by small atomic displacements, rendering these displacive transitions reversible. In contrast, elemental crystals, alloys, and :simple minerals will exhibit reconstructive "bond-breaking" transitions. Here we show that reconstructive transition occurs in the heteroanionic compound KNaNbOF5, owing to reorientations of the [NbOF5](2-) units that trigger a reconfiguration of the cation lattice. Using a combination of synchrotron based measurements empirical dynamic simulations, and ab initio calculations, we report structure changes across the transition and formulate an atomistic minimum energy transition path to explain its irreversible nature. Our results indicate that multianionic compounds are likely to host reconstructive transitions that are frequently difficult to study and functionalize in simpler compounds. We anticipate that our insight into the forces that drive the transition will also lead to novel methods to control the assembly of structures in the solid state.
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Details
- Title
- Reconstructive Transitions from Rotations of Rigid Heteroanionic Polyhedra
- Creators
- Michael Holland - Northwestern UniversityNenian Charles - Drexel UniversityJames M. Rondinelli - Northwestern UniversityKenneth R. Poeppelmeier - Northwestern UniversityArgonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Publication Details
- Journal of the American Chemical Society, v 138(36), pp 11882-11889
- Publisher
- American Chemical Society; Washington, DC
- Number of pages
- 8
- Grant note
- DE-AC02-06CH11357 / DOE Office of Science by Argonne National Laboratory; United States Department of Energy (DOE) DMR-1608218; DMR-1307698; DMR-1454688; DMR-1100085 / National Science Foundation; National Science Foundation (NSF) 1307698 / Division Of Materials Research; National Science Foundation (NSF); NSF - Directorate for Mathematical & Physical Sciences (MPS) 1454688 / Direct For Mathematical & Physical Scien; National Science Foundation (NSF); NSF - Directorate for Mathematical & Physical Sciences (MPS)
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Materials Science and Engineering
- Web of Science ID
- WOS:000383410700061
- Scopus ID
- 2-s2.0-84987802589
- Other Identifier
- 991019330793704721
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- Collaboration types
- Domestic collaboration
- Web of Science research areas
- Chemistry, Multidisciplinary