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ReportsSpin Conservation Accounts for Aluminum Cluster Anion Reactivity Pattern with O2
The reactivity pattern of small (
1 Institute of Inorganic Chemistry, University of Karlsruhe (TH), 76128 Karlsruhe, Germany. 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.
2 Departments of Chemistry and Materials Science, Johns Hopkins University, Baltimore, MD 21218, USA. 3 Department of Physics, University of Konstanz, 78457 Konstanz, Germany. 4 Department of Chemistry, McNeese State University, Lake Charles, LA 70605, USA. 5 Department of Physics, Virginia Commonwealth University, Richmond, VA 23284, USA. * To whom correspondence should be addressed. E-mail: schnoeckel{at}chemie.uni-karlsruhe.de
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Science. ISSN 0036-8075 (print), 1095-9203 (online)
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