Assessment of interstitial potentials for rapid prediction of absolute band energies in crystals

Liam Harnett-Caulfield, Aron Walsh

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1 Citation (Scopus)


Electronic band alignment is a demanding process for first-principles simulations, but an important factor in materials selection for applications including electrocatalysis and photoelectrochemistry. Here, we revisit a bulk alignment procedure, originally developed by Frensley and Kroemer, using modern computational tools. The electrostatic potential in the interstitial region, obtained from density functional theory, with four exchange correlation functionals, is used to predict the valence band offsets of 27 zinc blende semiconductors. The results are found to be in qualitative agreement with Frensley and Kroemer’s original data. In addition to absolute electron energies, the possibility of extracting effective ionic charges is investigated and compared to Bader partial charges. With further developments, such a procedure may support rapid screening of the bulk ionization potential and electron affinity of crystals, as we illustrate with an extension to rock salt and perovskite structure types.

Original languageEnglish
Article number024113
JournalJournal of Chemical Physics
Issue number2
Publication statusPublished - 2021 Jul 14

Bibliographical note

Funding Information:
We acknowledge the contributions of Daniel W. Davies and Young-Kwang Jung for the compilation of the initial zinc blende structure set. We also acknowledge useful discussions with Keith T. Butler, Matthew Okenyi, and Matthias J. Golomb. This project was supported by the Plastic Electronics Centre for Doctoral Training, and calculations were facilitated by the Imperial College London Research Computing Service. We are grateful to the UK Materials and Molecular Modeling Hub for computational resources, which is partially funded by the EPSRC (Grant No. EP/T022213/1).

Publisher Copyright:
© 2021 Author(s).

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry


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