Using ultraviolet photoelectron spectroscopy, we provide direct experimental evidence that di-oxygen species are stable on anionic gold dimer and tetramer clusters at room temperature. The stabilization of molecular oxygen is crucial for the high activities of the low-temperature reactions on gold catalysts.

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The reactivity pattern of small (approximately 10 to 20 atoms) anionic aluminum clusters with oxygen has posed a long-standing puzzle. Those clusters with an odd number of atoms tend to react much more slowly than their even-numbered counterparts. We used Fourier transform ion cyclotron resonance mass spectrometry to show that spin conservation straightforwardly accounts for this trend. The reaction rate of odd-numbered clusters increased appreciably when singlet oxygen was used in place of ground-state (triplet) oxygen. Conversely, monohydride clusters AlnH-, in which addition of the hydrogen atom shifts the spin state by converting formerly open-shell structures to closed-shell ones (and vice versa), exhibited an opposing trend: The odd-n hydride clusters reacted more rapidly with triplet oxygen. These findings are supported by theoretical simulations and highlight the general importance of spin selection rules in mediating cluster reactivity.