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We have examined the valence-band electronic structures of gold and silver inthe same column in the periodic table with nominally filled d orbitals by meansof a recently developed polarization-dependent hard x-ray photoemission.Contrary to a common expectation, it is found that the 5d-orbital electronscontribute prominently to the conduction electrons in gold while the conductionelectrons in silver are to some extent free-electron-like with negligible 4dcontribution, which could be related to a well-known fact that gold is morestable than silver in air. The 4d electron correlation effects are found to beessential for the conduction electron character in silver.

Prominent 5d-orbital contribution to the conduction electrons in gold