The Reaction Rates of O2 with Closed-Shell and Open-Shell Alx鈥?/sup> and Gax鈥?/sup> Clusters under Single-Collision Conditions: Experimental an
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- 作者：Marco Neumaier ; Matthias Olzmann ; Boggavarapu Kiran ; Kit H. Bowen ; Bryan Eichhorn ; Sarah T. Stokes ; Angela Buonaugurio ; Ralf Burgert ; Hansgeorg Schn枚ckel
- 刊名：Journal of the American Chemical Society
- 出版年：2014
- 出版时间：March 5, 2014
- 年：2014
- 卷：136
- 期：9
- 页码：3607-3616
- 全文大小：405K
- 年卷期：v.136,no.9(March 5, 2014)
- ISSN：1520-5126
文摘
In order to characterize the oxidation of metallic surfaces, the reactions of O2 with a number of Alx鈥?/sup> and, for the first time, Gax鈥?/sup> clusters as molecular models have been investigated, and the results are presented here for x = 9鈥?4. The rate coefficients were determined with FT-ICR mass spectrometry under single-collision conditions at O2 pressures of 10鈥? mbar. In this way, the qualitatively known differences in the reactivities of the even- and odd-numbered clusters toward O2 could be quantified experimentally. To obtain information about the elementary steps, we additionally performed density functional theory calculations. The results show that for both even- and odd-numbered clusters the formation of the most stable dioxide species, [MxO2]鈭?/sup>, proceeds via the less stable peroxo species, [Mx+路路路O22鈥?/sup>]鈭?/sup>, which contains M鈥揙鈥揙鈥揗 moieties. We conclude that the formation of these peroxo intermediates may be a reason for the decreased reactivity of the metal clusters toward O2. This could be one of the main reasons why O2 reactions with metal surfaces proceed more slowly than Cl2 reactions with such surfaces, even though O2 reactions with both Al metal and Al clusters are more exothermic than are reactions of Cl2 with them. Furthermore, our results indicate that the spin-forbidden reactions of 3O2 with closed-shell clusters and the spin-allowed reactions with open-shell clusters to give singlet [Mx+路路路O22鈥?/sup>]鈭?/sup> are the root cause for the observed even/odd differences in reactivity.