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Title: Negative thermal expansion correlated with polyhedral movements and distortions in orthorhombic Y{sub 2}Mo{sub 3}O{sub 12}

Graphical abstract: Our work confirms the negative thermal expansion (NTE) behavior of the orthorhombic Y{sub 2}Mo{sub 3}O{sub 12} in this range 0–1000 K. The orthorhombic Y{sub 2}Mo{sub 3}O{sub 12} has an open framework structure where MoO{sub 4} tetrahedra and YO{sub 6} octahedra are connected by oxygen atoms. The previous mechanisms for the NTE behavior of orthorhombic Y{sub 2}Mo{sub 3}O{sub 12} are that the translational mode (see (b)) of the O bridge atoms in Y-O-Mo linkages will cause the linkages to be bent, reducing the space between polyhedra and making the volumetric shrinkage. Furthermore, the internal polyhedral distortions have been reported experimentally. It is necessary to reveal the relationship between NTE and polyhedral movements, distortions. From the vibrational properties, we get that the different vibrational eigenvectors of oxygen atoms relative to Y or Mo atoms can lead internal polyhedra to distort unevenly (see (c)). Herein, an extended 3D model of the connected unit YO{sub 6}-MoO{sub 4} based on the Y-O-Mo linkage is proposed (see (a)). It presents a simultaneous dynamic process, i.e. the YO{sub 6} octahedra and MoO{sub 4} tetrahedra distort unevenly, along with both polyhedra being closer which makes the volumetric contraction. This model is helpful to improve the mechanismsmore » of NTE and may be applied in the whole A{sub 2}M{sub 3}O{sub 12} family. - Highlights: • The NTE properties of Y{sub 2}Mo{sub 3}O{sub 12} are confirmed using a first-principles calculation. • The optical branch with the lowest frequency is most responsible for the NTE. • The relationship between NTE and polyhedral movements, distortions is elucidated. • An extended 3D model of the connected unit YO{sub 6}-MoO{sub 4} is proposed. - Abstract: The internal polyhedral distortions have been reported experimentally in orthorhombic Y{sub 2}Mo{sub 3}O{sub 12} as a negative thermal expansion (NTE) material. To reveal the relationship between NTE and polyhedral movements, distortions, the vibrational properties of Y{sub 2}Mo{sub 3}O{sub 12} have been studied using first-principles calculations. The lowest optical branch corresponding to translational mode of the O bridge atom in Y-O-Mo linkage has the largest negative Grüneisen parameter and therefore contributes most to the NTE behavior. The different vibrational eigenvectors of oxygen atoms relative to Y or Mo atoms can cause internal polyhedral to distort unevenly. Herein, an extended 3D model of the connected unit YO{sub 6}-MoO{sub 4} based on the Y-O-Mo linkage presents a simultaneous dynamic process, i.e. the YO{sub 6} octahedra and MoO{sub 4} tetrahedra distort unevenly, along with both polyhedra being closer which makes the volumetric contraction. This model is helpful to improve the mechanisms of NTE and may be applied in the whole A{sub 2}M{sub 3}O{sub 12} family.« less
Authors:
 [1] ; ; ; ;  [1] ;  [2] ;  [1] ;  [2] ;  [3]
  1. International Laboratory for Quantum Functional Materials of Henan, Zhengzhou University, Zhengzhou 450001 (China)
  2. (China)
  3. Department of Chemistry, University College London, London WC1H 0AJ (United Kingdom)
Publication Date:
OSTI Identifier:
22290484
Resource Type:
Journal Article
Resource Relation:
Journal Name: Materials Research Bulletin; Journal Volume: 48; Journal Issue: 7; Other Information: Copyright (c) 2013 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ATOMS; MOLYBDATES; ORTHORHOMBIC LATTICES; OXYGEN; THERMAL EXPANSION; YTTRIUM