The size-dependent influence of palladium doping on the structures of cationic gold clusters†
| Autor: | Olga V. Lushchikova, Gao-Lei Hou, Francesca Baletto, Piero Ferrari, Joost M. Bakker, Ewald Janssens, Laia Delgado-Callico |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Technology
Materials science ADSORPTION Infrared ARGON Chemistry Multidisciplinary Materials Science chemistry.chemical_element Bioengineering Materials Science Multidisciplinary 02 engineering and technology 010402 general chemistry 01 natural sciences Spectral line Dissociation (chemistry) Cluster (physics) General Materials Science Nanoscience & Nanotechnology Spectroscopy FELIX Condensed Matter Physics PROPENE Science & Technology SPECTROSCOPY Doping General Engineering AU-20 General Chemistry 021001 nanoscience & nanotechnology Atomic and Molecular Physics and Optics 3. Good health 0104 chemical sciences Chemistry chemistry Chemical physics Physical Sciences Science & Technology - Other Topics Density functional theory AU-N(+) 0210 nano-technology Palladium |
| Zdroj: | Nanoscale Advances Nanoscale Advances, 3, 6197-6205 Nanoscale Advances, 3, pp. 6197-6205 |
| ISSN: | 2516-0230 |
| Popis: | The physicochemical properties of small metal clusters strongly depend on their precise geometry. Determining such geometries, however, is challenging, particularly for clusters formed by multiple elements. In this work, we combine infrared multiple photon dissociation spectroscopy and density functional theory calculations to investigate the lowest-energy structures of Pd doped gold clusters, PdAun−1+ (n ≤ 10). The high-quality experimental spectra allow for an unambiguous determination of the structures adopted by the clusters. Our results show that the Pd–Au interaction is so large that the structures of PdAun−1+ and Aun+ are very different. Pd doping induces a 2D to 3D transition at much smaller cluster sizes than for pure Aun+ clusters. PdAun−1+ clusters are three-dimensional from n = 4, whereas for Aun+ this transition only takes place at n = 7. Despite the strong Au–Pd interaction, the Aun−1+ cluster geometries remain recognizable in PdAun−1+ up to n = 7. This is particularly clear for PdAu6+. In PdAu8+ and PdAu9+, Pd triggers major rearrangements of the Au clusters, which adopt pyramidal shapes. For PdAu4+ we find a geometry that was not considered in previous studies, and the geometry found for PdAu8+ does not correspond to the lowest-energy structure predicted by DFT, suggesting kinetic trapping during formation. This work demonstrates that even with the continuous improvement of computational methods, unambiguous assignment of cluster geometries still requires a synergistic approach, combining experiment and computational modelling. The physicochemical properties of small metal clusters strongly depend on their precise geometry. |
| Databáze: | OpenAIRE |
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