Bonding Nature between Noble Gases and Small Gold Clusters.

Noble gases are usually seen as utterly inert, likewise gold, which is typically conceived as the noblest of all metals. While one may expect that noble gases bind to gold via dispersion interactions only, strong bonds can be formed between noble gas atoms and small gold clusters. We combine mass spectrometry, infrared spectroscopy, and density functional theory calculations to address the bonding nature between Aun+ (n ≤ 4) clusters and Ar, Kr, and Xe. We unambiguously determine the geometries and quantitatively uncover the bonding nature in AunNgm+ (Ng = Ar, Kr, Xe) complexes. Each Au cluster can form covalent bonds with atop bound noble gas atoms, with strengths that increase with the noble gas atomic radius. This is demonstrated by calculated adsorption energies, Bader electron charges, and analysis of the electron density. The covalent bonding character, however, is limited to the atop-coordinated Ng atoms.

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

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, PdAu n-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 PdAu n-1 + and Au n + are very different. Pd doping induces a 2D to 3D transition at much smaller cluster sizes than for pure Au n + clusters. PdAu n-1 + clusters are three-dimensional from n = 4, whereas for Au n + this transition only takes place at n = 7. Despite the strong Au-Pd interaction, the Au n-1 + cluster geometries remain recognizable in PdAu n-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.

A universal signature in the melting of metallic nanoparticles.

Predicting when phase changes occur in nanoparticles is fundamental for designing the next generation of devices suitable for catalysis, biomedicine, optics, chemical sensing and electronic circuits. The estimate of the temperature at which metallic nanoparticles become liquid is, however, a challenge and a standard definition is still missing. We discover a universal feature in the distribution of the atomic-pair distances that distinguishes the melting transition of monometallic nanoparticles. We analyse the solid-liquid change of several late-transition metals nanoparticles, i.e. Ni, Cu, Pd, Ag, Au and Pt, through classical molecular dynamics. We consider various initial shapes from 146 to 976 atoms, corresponding to the 1.5-4.1 nm size range, placing the nanoparticles in either a vacuum or embedded in a homogeneous environment, simulated by an implicit force-field. Regardless of the material, its initial shape, size and environment, the second peak in the pair-distance distribution function, expected at the bulk lattice distance, disappears when the nanoparticle melts. As the pair-distance distribution is a measurable quantity, the proposed criterion holds for both numerical and experimental investigations. For a more straightforward calculus of the melting temperature, we demonstrate that the cross-entropy between a reference solid pair-distance distribution function and the one of nanoparticles at increasing temperatures present a quasi-first order transition at the phase-change temperature.

Stability of cationic silver doped gold clusters and the subshell-closed electronic configuration of AgAu14.

Silver doping is a valuable route to modulate the structural, electronic, and optical properties of gold clusters. We combine photofragmentation experiments with density functional theory calculations to investigate the relative stability of cationic Ag doped Au clusters, AgAuN-1 + (N ≤ 40). The mass spectra of the clusters after photofragmentation reveal marked drops in the intensity of AgAu8 +, AgAu14 +, and AgAu34 +, indicating a higher relative stability of these sizes. This is confirmed by the calculated AgAuN-1 + (N ≤ 17) dissociation energies peaking for AgAu6 +, AgAu8 +, and AgAu14 +. While the stability of AgAu6 + and AgAu8 + can be explained by the accepted electronic shell model for metal clusters, density of states analysis shows that the geometry plays an important role in the higher relative stability of AgAu14 +. For this size, there is a degeneracy lifting of the 1D shell, which opens a relatively large HOMO-LUMO gap with a subshell-closed 1S21P41P21D6 electronic configuration.