Skin-depth lattice strain, core-level trap depression and valence charge polarization of Al surfaces

Abstract

Clarifying the origin for surface core-level shift (SCLS) and gaining quantitative information regarding the coordination-resolved local strain, binding energy (BE) shift and cohesive energy change have been a challenge. Here, we show that a combination of the bond order–length–strength (BOLS) premise, X-ray photoelectron spectroscopy (XPS) and the ab initio density functional theory (DFT) calculations of aluminum (Al) [Formula: see text] energy shift of Al surfaces has enabled us to derive such information, namely, (i) the [Formula: see text] energy of an isolated Al atom [Formula: see text] and its bulk shift (0.499 eV); (ii) the skin lattice contracts by up to 12.5% and the BE density increases by 70%; and (iii) the cohesive energy drops up to 38%. It is affirmed that the shorter and stronger bonds between under-coordinated atoms provide a perturbation to the Hamiltonian and hence lead to the local strain, quantum entrapment and valence charge polarization. Findings should help in understanding the phenomena of surface pre-melting and skin-high elasticity, in general.