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Small copper-oxide cluster cations, namely, CuOAr +  and Cu 2 O 2  + , are studied by mass spectrometry and X-ray absorption spectroscopy (XAS) to investigate the oxidation state of copper atoms. The XAS in Cu L 3 -region revealed that the oxidation number of Cu is almost +2.1 and +2.3 for CuOAr +  and Cu 2 O 2  + , respectively, which are consistent with the natural charges obtained by quantum chemical calculation. It was also revealed that the binding energy of Ar to CuO +  is unexpectedly high to form CuOAr +  dominantly as a result of a significant amount of charge transfer to the Ar atom.

X-ray absorption spectroscopy of small copper-oxide cluster ions for analyses of Cu oxidation state and Ar complexation: CuOAr + and Cu 2 O 2 +