Chemisorption-induced two- to three-dimensions structural transformations in gold pentamer (CO)nAu5– (n =0–5)

• Published in: Journal of molecular modeling 2014-11, Vol.20 (11), Article 2490
• Main Authors: Zhong, Ming-Min, Kuang, Xiao-Yu, Wang, Zhen-Hua, Yuan, Hong-kuan, Chen, Hong
• Format: Article
• Language: English
• Subjects: Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Molecular Medicine; Original Paper; Theoretical and Computational Chemistry
• ISSN: 1610-2940; 0948-5023
• DOI: 10.1007/s00894-014-2490-3

Understanding the geometry structures of gold clusters, especially with adsorbates, is essential for designing highly active gold nanocatalysts. Here, CO chemisorption onto the Au 5 – cluster is investigated using the density functional calculations. It is found that chemisorption of CO molecules can induce previously unreported two- to three-dimensions (3D) structural changes. Even a single CO chemisorption induces a major structural change to explain the huge blue-shift in photoelectron spectroscopy (PES). The apex site in the parent Au 5 – cluster is not always the most preferred site for the chemisorption, and two bridged adsorption CO molecules are observed in the lowest-energy (CO) 3 Au 5 – cluster. A clear splitting is observed in the first PES of (CO) 4 Au 5 – , and calculated planar and 3D geometries are likely coexisting in the cluster beam. The fifth CO adsorption leads to the structural transformation of Au 5 skeleton to create more apex sites to accommodate five CO molecules. The structural properties, together with the vertical electron detachment energy (VDE) and binding energies calculations indicate that the chemisorption-saturated number is 5.