Abstract

The electronic properties of gold–silver binary cluster anions (AunAgm−; 2⩽n+m⩽4) were studied by using photoelectron spectroscopy (PES) with a magnetic-bottle-type electron spectrometer. The AunAgm− cluster anions were generated by a laser vaporization of a gold–silver alloy rod. For triatomic AunAg3−n clusters, monotonous increases of electron affinity (EA) were observed by the replacement of Ag atom by Au atom. In contrast, the change in EA of tetratomic AunAg4−n clusters was irregular; for n=0–2 their EAs are almost the same around 1.5 eV, whereas for n=3,4 they increase to around 2.7 eV. This irregularity in EA of AunAg4−n can be attributed to the contribution of an ionic bonding. For Au1Ag3− and Au2Ag2−, moreover, the PES spectra show two components whose intensity ratio depends on cluster source conditions, showing that two isomers should coexist at these two compositions.

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