Prism rather than tetrahedron: low-energy structures for gaseous gold clusters Au10(O2)n + by density functional calculations

• Published in: Molecular physics Vol. 122; no. 4
• Main Authors: Liu, Yong, Liu, Cai-Ping, Mang, Chao-Yong, Wu, Ke-Chen
• Format: Journal Article
• Language: English
• Published: Abingdon Taylor & Francis 16.02.2024; Taylor & Francis Ltd
• Subjects: Adsorption; chemical adsorption; Chemical bonds; Clusters; Covalent bonds; Density functional theory; Energy; Energy of dissociation; Free energy; Gold; Heat of formation; Infrared spectroscopy; IR spectrum; Oxygen; oxygen adsorption; Single electrons; Tetrahedra
• ISSN: 0026-8976; 1362-3028
• DOI: 10.1080/00268976.2023.2252109

The purpose of this study is to reveal the adsorption mechanism of oxygen molecules on gold clusters. density functional theory is employed to investigate the low-energy structure of multiple O 2 adsorption on the Au 10 + cluster and findings are compared with IR spectra. The nature of bonding of the O 2 molecule and Au 10 + cluster has been characterised through several metrics like binding energy, dissociation energy, bond length, and vibrational frequencies. The result shows that the lowest-energy structures are prism-shaped rather than tetrahedron-shaped, where only one O 2 is chemically adsorbed while others are physically adsorbed. Chemically adsorbed η 2 -O 2 behaves like free O 2 - , forming a single electron π bond with Au 10 + , while physically adsorbed η 1 -O 2 does not result in an effective chemical bond and behaves like free O 2 . This study provides insights into the mechanism of oxygen molecule adsorption on gold clusters and can contribute to further research on the catalytic mechanism of gold clusters. Highlights Lowest energy structures are prism-shaped rather than tetrahedron-shaped, which is supported by IR spectrum and chemical hardness. Chemically adsorbed O 2 is activated and displays structural and spectral features of free O 2 - , while physically adsorbed O 2 is close to free O 2 in vibrational frequency and bond length. Chemical adsorption is equivalent to a single electron π bond while physical adsorption forms no effective chemical bond due to the lack of electronic pairing between Au 10 + and O 2 .