期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 25, 期 69, 页码 15795-15804出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201902794
关键词
adsorption; clusters; gas phase; gold; reaction
资金
- KU Leuven-Budapest University of Technology and Economics [CELSA/18/032]
- FWO (Research Foundation Flanders)
The dopant and size-dependent propene adsorption on neutral gold (Au-n) and yttrium-doped gold (Aun-1Y) clusters in the n = 5-15 size range are investigated, combining mass spectrometry and gas phase reactions in a low-pressure collision cell and density functional theory calculations. The adsorption energies, extracted from the experimental data using an RRKM analysis, show a similar size dependence as the quantum chemical results and are in the range of approximate to 0.6-1.2 eV. Yttrium doping significantly alters the propene adsorption energies for n = 5, 12 and 13. Chemical bonding and energy decomposition analysis showed that there is no covalent bond between the cluster and propene, and that charge transfer and other non-covalent interactions are dominant. The natural charges, Wiberg bond indices, and the importance of charge transfer all support an electron donation/back-donation mechanism for the adsorption. Yttrium plays a significant role not only in the propene binding energy, but also in the chemical bonding in the cluster-propene adduct. Propene preferentially binds to yttrium in small clusters (n<10), and to a gold atom at larger sizes. Besides charge transfer, relaxation also plays an important role, illustrating the non-local effect of the yttrium dopant. It is shown that the frontier molecular orbitals of the clusters determine the chemical bonding, in line with the molecular-like electronic structure of metal clusters.
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