Orbital Energy Spectra of Electrons in Chemisorption Bonds: O, S, Se on Ni(100)

TLDR: In this paper, the first experimental determinations of orbital energy spectra of electrons in chemisorption bonds were presented, and a transition density function which is essentially the local density of states in the surface region of the solid was determined.

Abstract: This work presents the first experimental determinations of orbital energy spectra of electrons in chemisorption bonds. Our method, ion neutralization spectroscopy, determines a transition density function which is essentially the local density of states in the surface region of the solid. For the particular surface formed by chemisorption of the chalcogens in ordered, surface‐crystalline arrays on Ni(100), the local density of states includes a strong component from the orbital energy spectrum of the electrons in the bonds of the surface molecules formed from the adsorbate atom and Ni atoms presented by the substrate lattice. The orbital levels of electrons in the surface bonds are broadened resonances or virtual states in whose energy range local wavefunction magnitude and hence transition probability for ion neutralization are enhanced. These orbital energy spectra, coupled with measurement of work‐function change on adsorption, suggest, in many instances, plausible identifications of local bonding str...