Valence band XPS spectra of K silicate glasses: Effect of HOMO energies on K, Na and Li leach rates, activation energies and reaction mechanism

Abstract

X-ray Photoelectron spectra of K-silicate glass valence bands (VBs) are composed of distinct upper and lower bands, separated by a minimum at ∼10 eV binding energy. A third, narrow band at ∼4.5 eV represents the highest energy occupied molecular orbitals (HOMOs). Na and Li glass VBs are similarly composed of upper, lower and HOMOs bands. The HOMOs reside only on NBO atoms (NBO = O atoms of the Si-O-M moiety; M = alkali), are non-bonding orbitals of O 2py character and are located at 4.5, 4.8 and 5.2 eV in K, Na and Li glasses. The order corresponds to alkali leach rates in water. We propose a SN reaction mechanism and Frontier Molecular Orbital concepts for leaching involving the HOMOs of the glasses and the LUMO of an adsorbed water molecule. The activated complex, Si-NBO*-M (NBO* = NBO•••HO-H), is formed through H-bonding of a solvent H2O molecule to NBO.