First-principles calculations of Cu(001) thin films: quantum size effect in surface energetics and surface chemical reactivities

TL;DR

This study uses first-principles calculations to explore quantum size effects in Cu(001) thin films, revealing oscillations in surface properties and adsorption energies that impact surface chemistry and catalysis.

Contribution

It provides a detailed analysis of quantum size effects on surface energetics and reactivity in Cu(001) films, including adsorption behavior of cesium, with results aligning with experimental data.

Findings

Quantum oscillations in surface energy and work function as a function of film thickness.

Large-amplitude oscillations in cesium adsorption energies.

Quantum size effects influence surface reactivity and catalysis potential.

Abstract

First-principles calculations of Cu(001) free-standing thin films have been performed to investigate the oscillatory quantum size effects exhibited in surface energy, work function, atomic relaxation, and adsorption energy of the cesium adsorbate. The quantum well states have been shown and clarified at particular $k$-points corresponding to the stationary extrema in bulk Brillouin zone, which are in good agreement with experimental observations. The calculated surface energetics and geometry relaxations are clearly featured by quantum oscillations as a function of the film thickness of the film with oscillation periods characterized by a superposition of long and short length scales. Furthermore, we have investigated Cs adsorption onto Cu(001) thin films as a function of the film thickness. Our systematic calculated results clearly show the large-amplitude quantum oscillations in adsorption energetics, which may be used to tailor catalysis, chemical reactions and other surface processes in nanostructured materials.