Non-covalent Interactions and Charge Transfer between Propene and Neutral Yttrium-Doped and Pure Gold Clusters.

ABSTRACT: The dopant and size-dependent propene adsorption on neutral gold (Au_n ) and yttrium-doped gold (Au_n-1 Y) 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 ?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.

SUBMITTER: Barabas J 

PROVIDER: S-EPMC6916555 | biostudies-literature | 2019 Dec

REPOSITORIES: biostudies-literature