Electronic structures of silver oxides

Abstract

The oxides of silver have a number of important technological applications, including use in battery technology, catalysis, and in the treatment of dermatological conditions. However, only the Ag2O phase has been well characterized in previous work. To this end, this paper characterizes the electronic structures of the major oxide forms, namely, Ag2O, Ag2O3, and AgO, using standard density functional theory (DFT), Hartree-Fock, and hybrid-DFT approaches. The optical properties are also assessed for these materials, enabling comparisons to be drawn to experiment and the origin of optical band gaps to be explained. The calculated optical gaps also suggest that electrodeposited Ag2O films may not consist of pure material. Hartree-Fock calculations are seen to fail to model Ag(I) species correctly, due to the neglect of correlation. DFT and hybrid-DFT methods are seen to perform better, but problems due to the lack of van der Waals interactions are identified. Preliminary calculations using empirical dispersion corrections are discussed.