GRADIENT CORRECTIONS IN DENSITY-FUNCTIONAL THEORY CALCULATIONS FOR SURFACES - CO ON PD(110)

P HU*, DA KING, S CRAMPIN, MH LEE, MC PAYNE

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

159 Citations (Scopus)

Abstract

Ab initio total energy calculations have been performed for CO chemisorption on Pd(110). Local density approximation (LDA) calculations yield chemisorption energies which are significantly higher than experimental values but inclusion of the generalised gradient approximation (GGA) gives better agreement. In general, sites with higher coordination of the adsorbate to surface atoms lead to a larger degree of overbinding with LDA, and give larger corrections with GGA. The reason is discussed using a first-order perturbation approximation. It is concluded that this may be a general failure of LDA for chemisorption energy calculations. This conclusion may be extended to many surface calculations, such as potential energy surfaces for diffusion.

Original languageEnglish
Pages (from-to)501-506
Number of pages6
JournalChemical Physics Letters
Volume230
Issue number6
Publication statusPublished - 09 Dec 1994

Keywords

  • TOTAL-ENERGY CALCULATIONS
  • MOLECULAR-DYNAMICS
  • ELECTRON-GAS
  • PSEUDOPOTENTIALS
  • APPROXIMATION
  • CHEMISORPTION
  • ADSORPTION
  • ALUMINUM
  • SITE

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