The size-dependent influence of palladium doping on the structures of cationic gold clusters

Piero Ferrari; Laia Delgado-Callico; Olga V. Lushchikova; Gao-lei Hou; Francesca Baletto; Joost M. Bakker; Ewald Janssens

doi:10.1039/D1NA00587A

The size-dependent influence of palladium doping on the structures of cationic gold clusters

Piero Ferrari, Laia Delgado-Callico, Olga V. Lushchikova, Gao-lei Hou, Francesca Baletto, Joost M. Bakker, Ewald Janssens

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2 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	6197-6205
Number of pages	9
Journal	Nanoscale Advances
Volume	3
Issue number	21
Early online date	21 Sept 2021
DOIs	https://doi.org/10.1039/D1NA00587A
Publication status	Published - 7 Nov 2021

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@article{1349e22cde6044f299f070e7f44e0cc3,

title = "The size-dependent influence of palladium doping on the structures of cationic gold clusters",

abstract = "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.",

author = "Piero Ferrari and Laia Delgado-Callico and Lushchikova, {Olga V.} and Gao-lei Hou and Francesca Baletto and Bakker, {Joost M.} and Ewald Janssens",

note = "Funding Information: This work has been supported by the KU Leuven Research Council (project C14/18/073) and by the Research Foundation-Flanders (FWO), project G0A0519N. The research leading to this result has been supported by the project CALIPSOplus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. P. F. acknowledges the FWO for a postdoctoral grant. We gratefully acknowledge the support to the FELIX Laboratory by the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO). The computational work has been performed under the Project HPC-EUROPA3 (INFRAIA-2016-1-730897), with the support of the EC Research Innovation Action under the H2020 Programme. We benet of the computer resources and technical support provided by EPCC at The University of Edinburgh. LDC is supported by King's College London through the NMES Faculty Studentship Scheme. LDC and FB are grateful to their membership of the UK's HEC Materials Chemistry Consortium funded by EPSRC (EP/R029431). This work used ARCHER2 UK National Supercomputing Service (http://www.archer2.ac.uk). They further acknowledge the UK Materials and Molecular Modelling Hub for computational resources, MMM Hub, which is partially funded by EPSRC (EP/P020194 and EP/T022213). FB thanks the nancial support offered by the Royal Society (No. RG 120207) and the technical support offered by the NMES Faculty at the King's College London to maintain local HPC facilities. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry.",

year = "2021",

month = nov,

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doi = "10.1039/D1NA00587A",

language = "English",

volume = "3",

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journal = "Nanoscale Advances",

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T1 - The size-dependent influence of palladium doping on the structures of cationic gold clusters

AU - Ferrari, Piero

AU - Delgado-Callico, Laia

AU - Lushchikova, Olga V.

AU - Hou, Gao-lei

AU - Baletto, Francesca

AU - Bakker, Joost M.

AU - Janssens, Ewald

N1 - Funding Information: This work has been supported by the KU Leuven Research Council (project C14/18/073) and by the Research Foundation-Flanders (FWO), project G0A0519N. The research leading to this result has been supported by the project CALIPSOplus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. P. F. acknowledges the FWO for a postdoctoral grant. We gratefully acknowledge the support to the FELIX Laboratory by the Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO). The computational work has been performed under the Project HPC-EUROPA3 (INFRAIA-2016-1-730897), with the support of the EC Research Innovation Action under the H2020 Programme. We benet of the computer resources and technical support provided by EPCC at The University of Edinburgh. LDC is supported by King's College London through the NMES Faculty Studentship Scheme. LDC and FB are grateful to their membership of the UK's HEC Materials Chemistry Consortium funded by EPSRC (EP/R029431). This work used ARCHER2 UK National Supercomputing Service (http://www.archer2.ac.uk). They further acknowledge the UK Materials and Molecular Modelling Hub for computational resources, MMM Hub, which is partially funded by EPSRC (EP/P020194 and EP/T022213). FB thanks the nancial support offered by the Royal Society (No. RG 120207) and the technical support offered by the NMES Faculty at the King's College London to maintain local HPC facilities. Publisher Copyright: © The Royal Society of Chemistry.

PY - 2021/11/7

Y1 - 2021/11/7

N2 - 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.

AB - 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.

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U2 - 10.1039/D1NA00587A

DO - 10.1039/D1NA00587A

M3 - Article

SN - 2516-0230

VL - 3

SP - 6197

EP - 6205

JO - Nanoscale Advances

JF - Nanoscale Advances

IS - 21

ER -

The size-dependent influence of palladium doping on the structures of cationic gold clusters

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