The photoelectron spectra of the small Au-Ag mixed clusters produced by the laser vaporization of their alloy rod were observed. It was found that in their anions, the replacement of an Ag atom by an Au atom accompanies a preferable substitution to accept the excess charging electron. In triatomic Au-Ag clusters, Au atoms existed as a terminal atom. Evidence was obtained that in tetratomic Au-Ag clusters, isomers can coexist due to the contribution from an ionic bonding character.
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