Aluminum Cluster Anion Reactivity with Singlet Oxygen: Evidence of Al9 – Stability

Recently, it was discovered that specific aluminum clusters (e.g., Al13 –) that demonstrate enhanced resistance to reactivity with oxygen may do so not only because of a closed electronic jellium shell as originally supposed but also because of a forbidden spin-flip in the transition state of the re...

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Veröffentlicht in:Journal of physical chemistry. C 2011-05, Vol.115 (20), p.9903-9908
Hauptverfasser: Woodward, W. Hunter, Eyet, Nicole, Shuman, Nicholas S, Smith, Jordan C, Viggiano, Albert A, Castleman, A. W
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Sprache:eng
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Zusammenfassung:Recently, it was discovered that specific aluminum clusters (e.g., Al13 –) that demonstrate enhanced resistance to reactivity with oxygen may do so not only because of a closed electronic jellium shell as originally supposed but also because of a forbidden spin-flip in the transition state of the reaction. Herein, we discuss an experiment using a multiple-species laminar flow reaction vessel coupled to a singlet oxygen generator. The present results suggest that all clusters react with singlet oxygen. Additionally, we observe Al9 –, a cluster previously unidentified as having any notable stability, as being resistant to reaction with triplet oxygen. Furthermore, we discuss a means of estimating rate constants in a multiple-species flow tube where the products and reactants do not allow the use of traditional methods.
ISSN:1932-7447
1932-7455
DOI:10.1021/jp2008418