Effect of Cr substitution on the electronic structure of CuAl1xCrxO2

David O. Scanlon, Aron Walsh, Benjamin J. Morgan, Graeme W. Watson, David J. Payne, and Russell G. Egdell
Phys. Rev. B 79, 035101 – Published 5 January 2009

Abstract

The geometries and electronic structures of CuAl1xCrxO2 have been investigated using density-functional theory with on-site corrections for strongly correlated systems (GGA+U) for x=0,12,1. Al is found to be well described within the ionic model, with a valence charge corresponding to a +3 oxidation state. Substituting Cr for Al is predicted to increase the density of states at the top of the valence band, in agreement with experimental x-ray photoemission spectroscopy data. Analysis of atom-projected densities of states and valence charges suggests that this is due to increased covalency between Cr and O; the valence charge for O in the Cu-O-(Al,Cr) subunits changes from 1.74 to 1.25 when Cr replaces Al. This produces an indirect oxygen-mediated change to the Cud states.

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  • Received 18 September 2008

DOI:https://doi.org/10.1103/PhysRevB.79.035101

©2009 American Physical Society

Authors & Affiliations

David O. Scanlon, Aron Walsh*, Benjamin J. Morgan, and Graeme W. Watson

  • School of Chemistry, Trinity College Dublin, Dublin 2, Ireland

David J. Payne and Russell G. Egdell

  • Department of Chemistry, Inorganic Chemistry Laboratory, Oxford University, South Park Road, Oxford OX1 3QR, United Kingdom

  • *Present address: National Renewable Energy Laboratory, Golden, CO 80401, USA.
  • Author to whom correspondence should be addressed; wastong@tcd.ie

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Issue

Vol. 79, Iss. 3 — 15 January 2009

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