Local probing of the surface chemical bond using X-ray emission spectroscopy

and CO on Ni(100), benzene on Ni(100) and Cu(110), and glycine adsorbed on Cu(110). New types of molecular states are observed which are directly related to the surface chemical bond. The long-accepted Blyholder model which is based on a frontier orbital concept cannot explain our results for N2 and CO chemisorption. We find it necessary to offer a new picture where changes in the whole molecular orbital framework have to be considered. We show that both π and σ type interactions are important in describing the bonding in benzene to metal surfaces. The future prospect is illustrated by the adsorption of the simplest amino acid, glycine, on Cu(110). The adsorbate has four different atomic centers where X-ray emission spectra are obtained, providing a unique view of the local electronic structure.