The structures of cationic gold clusters probed by far-infrared spectroscopy

Ferrari, Piero; Hou, Gao‐Lei; Lushchikova, Olga V.; Calvo, F.; Bakker, Joost M.; Janssens, Ewald

doi:10.1039/d0cp01613f

Cited by 25 publications

(61 citation statements)

References 39 publications

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“…The geometries of the complexes that have a single Ar atom adsorbed are depicted in Figure 2 . In all cases, Ar adopts an atop coordination in the lowest-energy configuration, and its presence hardly affects the geometries of the bare Au n + clusters [ 24 , 36 ]. The possibility that isomers with a different adsorption site for Ar are present in the molecular beam, or that there is fluxionality between different adsorption sites, cannot be excluded [ 27 ].…”

Section: Resultsmentioning

confidence: 99%

“…The geometries of the bare Au n + ( n = 3–20) clusters were adopted from previous works. Infrared multiple photon dissociation spectroscopy was used in conjunction with DFT calculations to determine the geometries of the n = 3–9 sizes in Reference [ 24 ], whereas an extensive global search of low-energy isomers was performed for the bare clusters up to n = 20 in Reference [ 36 ]. Here, we have adopted the bare cluster geometries determined in Reference [ 24 ] up to n = 9, and those from Reference [ 36 ] in the n = 10–20 size range.…”

Section: Methodsmentioning

confidence: 99%

“…Infrared multiple photon dissociation spectroscopy was used in conjunction with DFT calculations to determine the geometries of the n = 3–9 sizes in Reference [ 24 ], whereas an extensive global search of low-energy isomers was performed for the bare clusters up to n = 20 in Reference [ 36 ]. Here, we have adopted the bare cluster geometries determined in Reference [ 24 ] up to n = 9, and those from Reference [ 36 ] in the n = 10–20 size range. We note that in Reference [ 24 ], the same level of theory as applied here was selected and a benchmark analysis showed that it accurately describes the vibrational modes of Au n Ar m + clusters.…”

Section: Methodsmentioning

confidence: 99%

“…Here, we have adopted the bare cluster geometries determined in Reference [ 24 ] up to n = 9, and those from Reference [ 36 ] in the n = 10–20 size range. We note that in Reference [ 24 ], the same level of theory as applied here was selected and a benchmark analysis showed that it accurately describes the vibrational modes of Au n Ar m + clusters. To locate the preferred Ar adsorption sites, Ar was then placed at all possible atop coordination positions, followed by geometry optimization.…”

Section: Methodsmentioning

confidence: 99%

“…The attachment of Ar (and other noble gas elements) to larger cationic gold clusters has been reported. For example, Ar has been used as a tagging/spectator atom when investigating the geometries and the optical absorption spectra of pure and doped gold clusters [ 24 , 25 , 26 , 27 , 28 ]. Moreover, in investigations of the optical absorption of Au n + clusters in the n = 13–20 size range, Xe was employed as the tagging element instead of Ar, as the interaction of the latter noble gas element was seen to decrease with cluster size and therefore, it was easier to form the complexes with Xe [ 29 ].…”

Section: Introductionmentioning

confidence: 99%

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Argon Adsorption on Cationic Gold Clusters Aun+ (n ≤ 20)

Ferrari¹,

Janssens²

2021

Molecules

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The interaction of Aun+ (n ≤ 20) clusters with Ar is investigated by combining mass spectrometric experiments and density functional theory calculations. We show that the inert Ar atom forms relatively strong bonds with Aun+. The strength of the bond strongly varies with the cluster size and is governed by a fine interplay between geometry and electronic structure. The chemical bond between Aun+ and Ar involves electron transfer from Ar to Au, and a stronger interaction is found when the Au adsorption site has a higher positive partial charge, which depends on the cluster geometry. Au15+ is a peculiar cluster size, which stands out for its much stronger interaction with Ar than its neighbors, signaled by a higher abundance in mass spectra and a larger Ar adsorption energy. This is shown to be a consequence of a low-coordinated Au adsorption site in Au15+, which possesses a large positive partial charge.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Argon Adsorption on Cationic Gold Clusters Aun+ (n ≤ 20)

Ferrari¹,

Janssens²

2021

Molecules

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Benchmarking density functional theory methods for modelling cationic metal–argon complexes

et al. 2021

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Noble gas chemistry is fascinating because noble gases can make formal chemical bonds with metal ions, despite their closed electronic configuration. Argon-metal ion complexes are particularly interesting since their bonding is halfway between dispersion and covalent interactions. Although many metal ion-noble gas complexes have been synthesized, there are still disagreeing theoretical descriptions about their bonding, which is not yet fully understood. Accurate experimental data is important as solid reference for theoretical methodologies, but such data is currently scarce for complexes of metal ion with noble gas atoms. We measured infrared spectra of MArn + (n = 3-5; M = Au, Ag, Pd) complexes and use these spectra as benchmark data for different theory levels within the density functional theory formalism. Several basis sets, exchange-correlation functionals, and the inclusion of dispersion corrections were considered. The agreement between the measured spectra and the calculations strongly depends on the applied level of theory. Functionals of a higher level of complexity do not consistently provide a better agreement with the experiment; this is particularly the case for the B3LYP hybrid functional that performs worse than the PBE GGA functional. On the other hand, the inclusion of dispersion corrections and the use of a large basis sets are crucial for a good description of the interaction between M + and Arn.

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Ligand-protected gold nanoclusters probed by IRMPD spectroscopy and quantum chemistry calculations

Nieuwjaer

Beydoun

Lecomte

et al. 2022

Journal of Molecular Spectroscopy

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This paper reports an attempt to structurally characterize isolated ligand-protected gold nanoclusters by means of gas-phase InfraRed Multiple Photon Dissociation (IRMPD) spectroscopy compared to quantum chemistry Density Functional Theory (DFT) calculations. The mass-selected kilodalton nanocluster complexes consist of ten or eleven gold atoms that are bound to glutathione or phosphine ligands and are produced by ElectroSpray Ionization (ESI) in the form of multiply charged anions or cations. This study allows us to build some methodology benchmarks for species that are large for IRMPD experiments and that are used for biochemistry applications. These gas-phase results on isolated ions are compared to condensed phase data from Fourier-Transform InfraRed (FTIR) spectroscopy and to theoretical IR spectra that are calculated with two different functional/basis sets, namely B3LYP/6-31G* and M06L/LanL2DZ, at the scaled static harmonic level. Although theoretical calculations are able to reproduce well the experimental IR spectra, the size of such species and the presence of many possible interactions between ligands make difficult a precise assignment among the many possible molecular arrangements.

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The structures of cationic gold clusters probed by far-infrared spectroscopy

Abstract: Far-infrared multiple photon dissociation spectroscopy is used in combination with density functional theory calculations to determine the structures of isolated Aun+ (n ≤ 9) clusters.

Cited by 25 publications

References 39 publications

Argon Adsorption on Cationic Gold Clusters Aun+ (n ≤ 20)

Argon Adsorption on Cationic Gold Clusters Aun+ (n ≤ 20)

Benchmarking density functional theory methods for modelling cationic metal–argon complexes

Ligand-protected gold nanoclusters probed by IRMPD spectroscopy and quantum chemistry calculations

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