Chapter 8. Theory: Periodic Electronic Structure Calculations

  1. Prof. S. David Jackson and
  2. Dr. Justin S. J. Hargreaves
  1. Rudy Coquet1,
  2. Kara L. Howard2 and
  3. David J. Willock2

Published Online: 26 MAR 2009

DOI: 10.1002/9783527626113.ch8

Metal Oxide Catalysis

Metal Oxide Catalysis

How to Cite

Coquet, R., Howard, K. L. and Willock, D. J. (2008) Theory: Periodic Electronic Structure Calculations, in Metal Oxide Catalysis (eds S. D. Jackson and J. S. J. Hargreaves), Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany. doi: 10.1002/9783527626113.ch8

Editor Information

  1. University of Glasgow, Department of Chemistry, WestCHEM, Joseph Black Building, Glasgow, G12 8QQ, United Kingdom

Author Information

  1. 1

    Fuel Research Laboratory, Research & Development, Division Nippon Oil Corporation, 8, Chidoricho, Naka-ku, Yokohama, 231-0815, Japan

  2. 2

    Cardiff University, School of Chemistry, Main Building, Park Place, Cardiff, CF10 3AT, United Kingdom

Publication History

  1. Published Online: 26 MAR 2009
  2. Published Print: 15 OCT 2008

ISBN Information

Print ISBN: 9783527318155

Online ISBN: 9783527626113



  • Hartree–Fock approximation;
  • periodic quantum chemistry;
  • surface structure calculations;
  • oxide surface defects;
  • density functional theory;
  • band theory


In this chapter we cover the application of quantum chemistry to gain an understanding of the properties of oxide materials commonly used in catalysis. We begin with the background concepts of Hartree Fock and density function theories concentrating on their treatment of the electron-electron interaction through exchange and correlation energies. The emphasis of this contribution is the use of periodic boundary conditions and so there is then a resume of band theory.

The first set of examples cover oxide materials for which the oxidation state of the metal centers is easily determined. This includes the relative stability of the phases of alumina and its related hydroxides and a comparison of the surface structures of MgO and AI2O3. The stoichiometric surface of TiO2 is also included here.

For reducible oxides, in which electron localisation at transition metal cation sites is possible, we consider the relative merits of hybrid functionals and the DFT+U method drawing on TiO2, MoO3 and CeO2. These methods are shown to be required for a correct description of the defect structures that are known to be important in catalysis.