Mixed-Valency Signature in Vibrational Inelastic Electron Tunneling Spectroscopy

Abstract

Density functional theory simulations of the vibrational inelastic electron tunneling spectroscopy (IETS) of O2 on Ag(110) permits us to solve its unexplained IETS data [Hahn, Phys. Rev. Lett. 85, 1914 (2000)]. When semilocal density functional theory is corrected by including static intra-atomic correlations, the IETS simulations are in excellent agreement with the experiment. The unforeseen consequence of our calculations is that when adsorbed along the [001] direction, molecular O2 on Ag(110) is a mixed-valent system. This analysis of IETS unambiguously reveals the paramagnetic nature of O2 on Ag(110).