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小金团簇Au(n)(n = 1 - 7)与金红石TiO₂表面相互作用的密度泛函研究。I. 在化学计量表面上的吸附

Density functional study of the interaction between small Au clusters, Au(n) (n=1-7) and the rutile TiO(2) surface. I. Adsorption on the stoichiometric surface.

作者信息

Chrétien Steeve, Metiu Horia

机构信息

Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA.

出版信息

J Chem Phys. 2007 Aug 28;127(8):084704. doi: 10.1063/1.2770462.

Abstract

This is the first paper in a series of four dealing with the adsorption site, electronic structure, and chemistry of small Au clusters, Au(n) (n=1-7), supported on stoichiometric, partially reduced, or partially hydroxylated rutile TiO(2)(110) surfaces. Analysis of the electronic structure reveals that the main contribution to the binding energy is the overlap between the highest occupied molecular orbitals of Au clusters and the Kohn-Sham orbitals localized on the bridging and the in-plane oxygen of the rutile TiO(2)(110) surface. The structure of adsorbed Au(n) differs from that in the gas phase mostly because the cluster wants to maximize this orbital overlap and to increase the number of Au-O bonds. For example, the equilibrium structures of Au(5) and Au(7) are planar in the gas phase, while the adsorbed Au(5) has a distorted two-dimensional structure and the adsorbed Au(7) is three-dimensional. The dissociation of an adsorbed cluster into two adsorbed fragments is endothermic, for all clusters, by at least 0.8 eV. This does not mean that the gas-phase clusters hitting the surface with kinetic energy greater than 0.8 eV will fragment. To place enough energy in the reaction coordinate for fragmentation, the impact kinetic energy needs to be substantially higher than 0.8 eV. We have also calculated the interaction energy between all pairs of Au clusters. These interactions are small except when a Au monomer is coadsorbed with a Au(n) with odd n. In this case the interaction energy is of the order of 0.7 eV and the two clusters interact through the support even when they are fairly far apart. This happens because the adsorption of a Au(n) cluster places electrons in the states of the bottom of the conduction band and these electrons help the Au monomer to bind to the five-coordinated Ti atoms on the surface.

摘要

本文是关于负载在化学计量比、部分还原或部分羟基化的金红石型TiO₂(110)表面上的小尺寸金团簇Au(n)(n = 1 - 7)的吸附位点、电子结构及化学性质的系列四篇论文中的第一篇。电子结构分析表明,对结合能的主要贡献来自于金团簇的最高占据分子轨道与金红石型TiO₂(110)表面桥氧和面内氧上局域化的Kohn-Sham轨道之间的重叠。吸附的Au(n)的结构与气相中的结构不同,主要是因为团簇想要最大化这种轨道重叠并增加Au - O键的数量。例如,Au(5)和Au(7)在气相中的平衡结构是平面的,而吸附的Au(5)具有扭曲的二维结构,吸附的Au(7)是三维的。对于所有团簇,吸附的团簇分解为两个吸附片段都是吸热的,至少需要0.8 eV。这并不意味着动能大于0.8 eV撞击表面的气相团簇会发生碎片化。要在反应坐标中为碎片化放置足够的能量,撞击动能需要远高于0.8 eV。我们还计算了所有金团簇对之间的相互作用能。除了一个金单体与奇数n的Au(n)共吸附的情况外,这些相互作用都很小。在这种情况下,相互作用能约为0.7 eV,即使两个团簇相距较远,它们也会通过载体相互作用。发生这种情况是因为Au(n)团簇的吸附将电子置于导带底部的状态,这些电子有助于金单体与表面上五配位的Ti原子结合。

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