Using vibrationally resolved ultraviolet photoelectron spectroscopy, we studied oxygen adsorption on W monomer anions. Three oxygen atoms are atomically bound in a WO3 compound, whereas in WO4 the fourth oxygen atom is attached to the oxygen, forming a di-oxygen species, implying that atom to molecule transition of O2 takes place when the number of oxygen atoms attached to a W monomer anion exceeds three. Our results indicate that molecular adsorption of oxygen is preferred on electron-deficient metals, showing that the driving force of the atom to molecule transition for the chemisorption of diatomic molecules can be the variations of electronic structures of metal hosts.

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