A density-functional study of charge doping in WO3

Abstract

The addition of electron donors to the vacant A site of defect-perovskite structure tungsten trioxide causes a series of structural and chemical phase transitions; for instance, in the well-known case of the sodium tungsten bronzes (NaxWO3). Here we calculate the effect of the addition of electronic charge to WO3 without the complication of also including sodium ions. Our density functional theory method enables isolation of electronic effects from the additional size, chemical, and disorder effects present in experimental samples. Our calculated low-temperature phase diagram between x=0 and x=1 moves from the initial low-temperature monoclinic phase through a second (centered) monoclinic phase, an orthorhombic phase, a tetragonal antiferroelectric, and an aristotypic cubic phase, in broad agreement with the experimentally-observed transformations in NaxWO3. Our work confirms that the observed structural transformations are driven primarily by electronic factors. We find that the dominant electronic effect is the covalent interaction between the tungsten 5d and oxygen 2p orbitals.

REVTeX, 7 pages, 6 figures: to be submitted to Physical Review B. Preliminary results were presented as a poster at the European Meeting on Ferroelectrics, Cambridge, 2003 v2: no changes at all to content. Figures renamed to conform to what the Physical Review B upload server expects

References in corpus (4)

• The SIESTA method for ab initio order-N materials simulation
• Efficient index handling of multidimensional periodic boundary conditions
• Selfconsistent order-N density-functional calculations for very large systems
• Systematic generation of finite-range atomic basis sets for linear-scaling calculations

Cited by in corpus (16)

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• Density-functional studies of tungsten trioxide, tungsten bronzes, and related systems
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• First-principles re-investigation of bulk WO3
• First-Principles Study of Localised and Delocalised Electronic States in Crystallographic Shear Phases of Niobium Oxide
• The role of static disorder in negative thermal expansion in ReO3
• Superconducting Properties of the K${}_x$WO${}_3$ Tetragonal Tungsten Bronze and the Superconducting Phase Diagram of the Tungsten Bronze Family
• Density functionals and half-metalicity in La2/3Sr1/3MnO3
• Insulator to metal transition of WO3 epitaxial films induced by electrochemical Li-ion intercalation
• Influence of Lithium Interstitial Doping on the Optoelectronic Properties of NiO and WO${}_3$
• First-principles study of lattice dynamical properties of the room-temperature $P{2}_1/n$ and ground-state $P{2}_1/c$ phases of WO${}_3$
• Theoretical investigation of twin boundaries in WO${}_3$: Structure, properties and implications for superconductivity
• Transition Temperature of Superconductivity in Sodium Tungsten Bronze -Theoretical Study Based on First-principles Calculations-
• Coupling between octahedral rotations and local polar displacements in WO3/ReO3 superlattices
• Simplicity out of complexity: band structure for W${}_{20}$O${}_{58}$ superconductor
• Band structure of tungsten oxide W${}_{20}$O${}_{58}$ with ideal octahedra