Periodic density functional theory study of Pt(111): surface features of slabs of different thicknesses

Abstract

Bulk platinum and platinum slabs one to four (111) layers thick have been studied using the HF and DFT CO-LCAO (Hartree-Fock and density functional theory crystalline-orbital and linear-combination-of-atomic-orbitals) CRYSTAL program. The objective of this paper is to test the suitability of slabs of different thicknesses for modelling the (111) surface of platinum. The cohesive properties of the bulk (lattice constant, bulk modulus, cohesive energy) are reported and the electronic structure of the platinum bulk is discussed. The surface and relaxation energies as well as the relaxation distances of the slabs were evaluated. The electronic structure of the slabs is discussed in terms of Mulliken population analysis, the density of states, the band structure and electron-density difference maps. `Initial-state' surface-atom core-level shifts are reported, as well as atomic dipole and quadrupole moments perpendicular to the surface.