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