Interplay of Orbital and Relativistic Effects in Bismuth Oxyhalides: BiOF, BiOCl, BiOBr, and BiOI

Alex M. Ganose, Madeleine Cuff, Keith T. Butler, Aron Walsh, David O. Scanlon

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135 Citations (Scopus)


The BiOX (X = F, Cl, Br, and I) series were investigated using hybrid density functional theory with explicit treatment of spin-orbit coupling effects and dispersion interaction. First-principles calculations were performed in the framework of density functional theory (DFT). Special attention was paid to electron-electron interactions, relativistic effects, and dispersion interactions. All solid-state calculations were performed in a plane-wave basis set using the code VASP. Complete structural optimizations were performed at a series of volumes in order to calculate the equilibrium lattice parameters. Convergence with respect to k-point sampling and plane wave energy was checked, with a cutoff of 520 eV and a k-point density found to be sufficient. To align the electronic band energies to the vacuum level, a surface-slab model was constructed and the corresponding electrostatic potential averaged along the c-direction, using the MacroDensity package. The larger EA of BiOI also results in a reduced overpotential for O2/oxygen anion splitting and can explain why BiOI is not as active for the degradation of rhodamine B than BiOBr and BiOCl.

Original languageEnglish
Pages (from-to)1980-1984
Number of pages5
JournalChemistry of Materials
Issue number7
Publication statusPublished - 2016

Bibliographical note

Funding Information:
This work made use of the ARCHER UK National Supercomputing Service (, via our membership of the UK?s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202) and the UCL Legion HPC Facility (Legion@UCL). The work at UCL was supported by EPSRC (EP/N01572X/1). The work at Bath was supported by the ERC (Grant no. 277757) and the EPSRC (Grant no. EP/K016288/1, EP/L017792/1, and EP/M009580/1). D.O.S. acknowledges support from the SUPERSOLAR Solar Energy Hub (EP/J017361/1) for the provision of a flexible funding call award. A.M.G. acknowledges Diamond Light Source for the cosponsorship of a studentship on the EPSRC Centre for Doctoral Training in Molecular Modelling and Materials Science (EP/L015862/1). A.W. and D.O.S. acknowledge membership of the Materials Design Network.

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

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