| Autor: |
Shiv N. Khanna, Arthur C. Reber, Gabriel U. Gamboa |
| Rok vydání: |
2013 |
| Předmět: |
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| Zdroj: |
Journal of Physics: Conference Series. 438:012002 |
| ISSN: |
1742-6596 |
| DOI: |
10.1088/1742-6596/438/1/012002 |
| Popis: |
Theoretical studies have been carried out to investigate the unusual reactivity of Ag+15 cations with oxygen. Our previous work has shown that the reactivity of free metal clusters with oxygen entails a spin excitation that causes reduced reactivity in clusters with filled electronic shells and large HOMO-LUMO gaps. Earlier experiments on Ag+15 have shown that the cluster exhibits remarkable resistance to reactivity with oxygen despite having a valence electron count that is not expected to result in a filled electronic shell within the spherical jellium model. It is shown that Ag+15, Ag14, and Ag−13 clusters with 14 valence electrons, all have oblate bilayer atomic structures that lead to a splitting of the superatomic D-shell in a manner analogous to crystal field splitting of d-states in transition metals. The importance of the oblate structure is demonstrated by showing a correlation between an oblate deformation coefficient and the HOMO-LUMO gap of the different structures of Ag+15. The oblate deformation results in the splitting of the electronic subshells and leads to an unusually large HOMO-LUMO gap and the unusual resistance of the cationic species to oxidation. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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