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Angle-resolved photoemission was used to observe the electronic band structure of one and two monolayers of Hg on Ag(100). Evidence for new Hg electronic states and band structure arising from the hybridization of the atomic 5d5/2 orbitals is presented. Low-energy electron diffraction results indicate that the Hg overlayers assume the face-centered-cubic (fcc) structure of the Ag(100) substrate, which is not the natural (rhombohedral) structure of bulk Hg. The new electronic states are induced as a result of the bonding of Hg atoms with adjacent metal atoms.