Structures, Phase Stability, Amorphization, and Decomposition of V6O13 at High Pressures and Temperatures: Synthesis of Rutile-Related V0.92O2

Crystal Growth & Design, vol. 24, pp. 5582–5592

Abstract

The stability of mixed-valence V 6 O 13 at high pressures and high temperatures is studied experimentally in multianvil presses both ex situ and in situ using synchrotron energy-dispersive powder diffraction. V 6 O 13 starts to amorphize and decomposes above 18.5 GPa at room temperature. It transforms to rutile-related V 0.92 O 2 above 500 K in the pressure range up to about 15–17.5 GPa. The crystal structure of this new phase ( C 12/ m 1, Z = 4) was determined from laboratory single-crystal and powder X-ray diffraction data measured on single crystals grown at 10 GPa and 1373 K. The characteristic feature is the presence of two zigzag V–V chains. One of them has equidistant V atoms, while the other is with short and long V–V distances. In the average-ordered structure ( P 2/ m, Z = 2), both V–V chains are linear and equidistant. The M 2 polymorph of VO 2 is considered to be the ordered (though distorted) variant of V 0.92 O 2 . The experiments are complemented by density functional theory calculations and global explorations of the energy landscape of V 6 O 13 and V 0.92 O 2 compounds at high pressures using a multimethodological approach to construct and predict feasible structures.

Authors 12

1. Andrzej Grzechnik corresponding Aachen Institute of Crystallography

   Forschungszentrum Jülich · RWTH Aachen University

   Affiliation as printed

   Institute of Crystallography, RWTH Aachen University, Aachen D-52056, Germany

   Jülich Centre for Neutron Science-4 (JCNS-4), Forschungszentrum Jülich GmbH, Jülich D-52425, Germany

2. Branislav Viliam Hakala

   Forschungszentrum Jülich

   Affiliation as printed

   Jülich Centre for Neutron Science-2 (JCNS-2), Forschungszentrum Jülich GmbH, Jülich D-52425, Germany

3. Sophia Kurig Aachen Chair of Solid-State and Quantum Chemistry Institute of Inorganic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Chair of Solid-State and Quantum Chemistry, Institute of Inorganic Chemistry, RWTH Aachen University, Aachen D-52056, Germany

4. Nicolas P. Walte

   Heinz Maier-Leibnitz Zentrum · Technical University of Munich

   Affiliation as printed

   Heinz Maier-Leibnitz Zentrum (MLZ), Technische Universität München, Garching 85747, Germany

5. Noriyoshi Tsujino

   SPring-8 · Japan Synchrotron Radiation Research Institute

   Affiliation as printed

   Japan Synchrotron Radiation Research Institute/SPring-8, 1-1-1 Kouto, Sayo-cho, Sayo-gun 679-5198, Hyogo, Japan

6. Sho Kakizawa

   SPring-8 · Japan Synchrotron Radiation Research Institute

   Affiliation as printed

   Japan Synchrotron Radiation Research Institute/SPring-8, 1-1-1 Kouto, Sayo-cho, Sayo-gun 679-5198, Hyogo, Japan

7. Yuji Higo

   SPring-8 · Japan Synchrotron Radiation Research Institute

   Affiliation as printed

   Japan Synchrotron Radiation Research Institute/SPring-8, 1-1-1 Kouto, Sayo-cho, Sayo-gun 679-5198, Hyogo, Japan

8. Dejan Zagorac

   University of Belgrade · Vinča Institute of Nuclear Sciences

   Affiliation as printed

   Center for Synthesis, Processing and Characterization of Materials for Application in the Extreme Conditions, Belgrade 11001, Serbia

   Institute of Nuclear Sciences Vinča, Materials Science Laboratory, Belgrade University, Belgrade 11351, Serbia

9. Jelena Zagorac

   University of Belgrade · Vinča Institute of Nuclear Sciences

   Affiliation as printed

   Center for Synthesis, Processing and Characterization of Materials for Application in the Extreme Conditions, Belgrade 11001, Serbia

   Institute of Nuclear Sciences Vinča, Materials Science Laboratory, Belgrade University, Belgrade 11351, Serbia

10. Richard Dronskowski Aachen Chair of Solid-State and Quantum Chemistry Institute of Inorganic Chemistry

    RWTH Aachen University

    Affiliation as printed

    Chair of Solid-State and Quantum Chemistry, Institute of Inorganic Chemistry, RWTH Aachen University, Aachen D-52056, Germany

11. Johann Christian Schön

    Max Planck Institute for Solid State Research

    Affiliation as printed

    Max Planck Institute for Solid State Research, Stuttgart D-70569, Germany

12. Karen Friese Aachen Institute of Crystallography

    Forschungszentrum Jülich · RWTH Aachen University

    Affiliation as printed

    Institute of Crystallography, RWTH Aachen University, Aachen D-52056, Germany

    Jülich Centre for Neutron Science-2 (JCNS-2), Forschungszentrum Jülich GmbH, Jülich D-52425, Germany