Pressure cell-boundary relation, Fermi levels and surface dipoles for transition metals

Surface dipole barriers for transition metals have been deduced using calculated internal Fermi levels and experimental electron workfunctions. The internal Fermi levels are estimated from a survey of band structure calculations. They have been checked using a theorem which relates the pressure on a solid to the wavefunctions, their derivatives and energies at the Wigner-Seitz cell boundary. This theorem represents a generalization of a relation previously derived using statistical theory, which was used to provide an independent check on internal Fermi levels in simple metals by imposing the equilibrium, zero pressure condition. Reasonable agreement between band structure and pressure cell-boundary estimates for the transition metal internal Fermi level was obtained. The surface dipole barriers range from 0.2-0.44 Ryd (2.5-6 eV). Their large magnitude is a reflection of the large cell boundary electron densities for these metals.