0000000000314177
AUTHOR
Pentti Frondelius
Electronic, structural and chemical properties of gold clusters on ultra-thin oxide films
Two decades ago, it was found that gold is catalytically active as clusters although it is known to be inert as bulk material. In the work presented in this thesis, density functional theory calculations have been applied to show that the properties of gold clusters and small molecules, namely O2 and NO2, are di erent on oxide thin lms supported by metal carriers than on single crystal oxide surfaces. Collectively, these di erences are called thin- lm e ects. The e ects and the mechanisms behind them have been studied with atomistic calculations and rationalized with simple physical models. The signi cance of the thin- lm e ects for heterogeneous catalysis is discussed. It has been found th…
Charging of atoms, clusters, and molecules on metal-supported oxides: A general and long-ranged phenomenon
The density-functional theory is used to investigate the adsorption of Au atoms, Au clusters, and NO2 molecules on transition-metal-supported oxides. As compared to unsupported oxides, the adsorbates on supported oxide films are charged and experience a higher adsorption energy. The origin of the effect is explored by considering two different oxides (MgO and Al2O3) and a range of supporting metals. Moreover, the limits of the enhancement are probed by explicit calculations for thick MgO films and low coverage. The long-range character of the phenomenon is attributed to electrostatic polarization. The absolute strength depends on several contributions and their relative importance changes w…
Formation of Gold(I) Edge Oxide at Flat Gold Nanoclusters on an Ultrathin MgO Film under Ambient Conditions
Many active gold catalysts are prepared onreducible oxides, and strong interactions between the supportand the gold particle may create active sites at the peripheryclose to the particle–support interface. These interactionsmay also include charge transfer to or from the particle. Forpurely geometric reasons, small particles have a high propor-tion of low-coordinated edge and corner atoms that might actas reaction centers. Also, thermal effects from localized softphonon modes at particle edges may contribute to thelowering of critical reaction barriers.Lately, a large amount of work has been conducted toelucidate the properties of gold clusters on ultrathin (a fewmonolayers (ML) thick) MgO …
Adsorption and activation of O2 at Au chains on MgO/Mo thin films
We have investigated the adsorption of O(2) on Au(n) clusters (n = 1-6) supported by an ultra thin (3ML)MgO(001) film on Mo metal via density functional theory calculations. On thin films, these small clusters have chain like structures and their electronic states resemble 1D quantum well states. The Au(1-3) are charged by one electron whereas the larger Au(4-6) get two electrons from the substrate. This is confirmed both by the symmetries of the HOMO and LUMO states of the clusters and the Bader charge analysis. In contrast to the O(2) adsorption on gas-phase clusters, the adsorption energy of O(2) molecule does not show pronounced oscillations as a function of cluster size. The O(2) is ac…
Adsorption of small Au clusters on MgO and MgO/Mo: the role of oxygen vacancies and the Mo-support
We report a systematic density functional theory investigation of adsorption of small Aun (n = 1-6) clusters on ideal and defected MgO(100) single crystal surfaces and Mo(100) supported thin MgO(100) films. As a model defect, we consider a neutral surface oxygen vacancy (Fs). Optimal adsorption geometries and energies, cluster formation energies and cluster charges are discussed and compared in detail over four different substrates. For a given cluster size, the adsorption energy among these substrates increases in the order MgO, Fs/MgO, MgO/Mo and Fs/MgO/Mo. While cluster growth by association of atoms from gas phase is exothermic on all the substrates, cluster growth by diffusion and aggr…
Electronic structure of MgO-supported Au clusters: quantum dots probed by scanning tunneling microscopy.
We investigate via density functional theory (DFT) the appearance of small MgO-supported gold clusters with 8 to 20 atoms in a scanning tunneling microscope (STM) experiment. Comparison of simulations of ultrathin films on a metal support with a bulk MgO leads to similar results for the cluster properties relevant for STM. Simulated STM pictures show the delocalized states of the cluster rather than the atomic structure. This finding is due to the presence of s- derived delocalized states of the cluster near the Fermi energy. The properties of theses states can be understood from a jellium model for monovalent gold.
Quantum Well States in Two-Dimensional Gold Clusters on MgO Thin Films
The electronic structure of ultra-small Au clusters on thin MgO/Ag(001) films has been analyzed by scanning tunneling spectroscopy and density functional theory. The clusters exhibit two-dimensional (2D) quantum well states, whose shapes resemble the eigen-states of a 2D electron gas confined in a parabolic potential. From the symmetries of the HOMO and LUMO of a particular cluster, its electron filling and charge state is determined. In accordance to a DFT Bader-charge analysis, aggregates containing up to twenty atoms accumulate one to four extra electrons due to a charge transfer from the MgO/Ag interface. The HOMO - LUMO gap is found to close for clusters containing between 70 and 100 a…
Adsorption of gold clusters on metal-supported MgO: Correlation to electron affinity of gold
Adsorption of ${\mathrm{Au}}_{N}$ clusters $(N=1\char21{}6)$ on a bulk MgO(001) surface and on an ultrathin (3 ML) MgO(001) film supported by Mo metal is investigated via density-functional theory calculations. Comparison of the two substrates unambiguously shows that the gold clusters adsorbed on $\mathrm{Mg}\mathrm{O}∕\mathrm{Mo}$ turn into singly charged cluster anions ${\mathrm{Au}}_{N}^{\ensuremath{\delta}}$, $\ensuremath{\delta}\ensuremath{\approx}\ensuremath{-}1$. Their structures and internal charging patterns are analogous to singly charged, planar, gas-phase cluster anions ${\mathrm{Au}}_{N}^{\ensuremath{-}}$. The adsorption energy has prominent size-dependent odd-even oscillation…