Influence of confinement on atomic and molecular reactivity indicators in DFT

Abstract

Spatial confinement of atoms and molecules influences electronic structures, energy spectra, and chemical reactivity. A simple potential barrier approach involving a single parameter is used to study confinement in both atoms and molecules, focusing on the reactivity of the systems through the HOMO–LUMO gap, which is linked to the global chemical hardness. Both atoms and molecules are shown to respond with an increase in hardness when confined. The results suggest that previous observations of a HOMO–LUMO gap decrease for guest molecules in zeolites cannot be assigned exclusively to electron confinement.