DFT global optimisation of gas-phase and MgO-supported sub-nanometre AuPd clusters

Hussein, Heider A.; Davis, Jack B. A.; Johnston, Roy L.

doi:10.1039/c6cp03958h

Cited by 41 publications

(63 citation statements)

References 51 publications

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“…This is in disagreement with the 2D-3D transition point suggested by Zanti and Peeters at size N = 8 [35]. However, in continuation with the planar structural pattern observed for N = 4-10 Pd-doped Au clusters previously [37], the gas-phase Au 10 Pd 1 global minimum is also planar. A noncompact 3D structure is the GM for Au 11 Pd 1 .…”

Section: Pd11contrasting

confidence: 84%

“…Figure 4 shows the putative global minima for Pd clusters: their energies, coordinates and point groups are listed in Table S1 (see the Supporting Information). Similar to small Pd clusters [37], the lowest energy structures obtained here for medium-sized Pd clusters are all 3D. As for pure Au clusters, the structural motifs adopted by Pd clusters are size-dependent; for mediumsized Pd clusters, a structural transition occurs at N = 15 atoms from bilayer structures to filled cage structures.…”

Section: Au Clusterssupporting

confidence: 64%

“…Employing hybrid DFT, Zanti and Peeters [35] arrived at the same conclusion showing a 3D structure for N = 10. This, however, disagreed with the 2D Au 10 structure recently obtained by us [37] and previously by different research groups using semi-local density functional theory (DFT) [59] and coupled cluster singles doubles and perturbative triples [CCSD(T)] calculations [60,61]. Recently, Johansson et al, using a genetic algorithm and meta-GGA DFT, assigned a 3D structure as the GM structure at N = 12.…”

Section: Au Clustersmentioning

confidence: 66%

“…This even-odd behaviour is due to the fact that the Au atom has an unpaired s electron, and so reflects the greater stability of Au clusters (either 2D or 3D) with an even number of electrons, over those with an odd number [74][75][76][77]. The most stable cluster is 2D Au 12 , although its ∆ 2 E energy is lower (by 0.67 eV) than the magic size Au 6 observed recently [37]. Doping a single Pd atom into Au clusters shifts the stability from the even-number (N = 12, 14, and 16) clusters to odd-number (N = 11, 13, 15, and 17) clusters.…”

Section: Stabilitymentioning

confidence: 99%

“…In the Au-Pd system, doping an atom of one metal into a pure cluster of the other metal often yields clusters with non-identical structures and properties [35][36][37]. This can increase the difficulty in finding global minima, in addition to the permutational isomers (homotops) effect [38].…”

Section: Introductionmentioning

confidence: 99%

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Application of a parallel genetic algorithm to the global optimization of medium-sized Au–Pd sub-nanometre clusters

2018

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Abstract. To contribute to the discussion of the high activity and reactivity of Au-Pd system, we have adopted the BPGA-DFT approach to study the structural and energetic properties of medium-sized AuPd sub-nanometre clusters with 11-18 atoms. We have examined the structural behaviour and stability as a function of cluster size and composition. The study suggests 2D-3D crossover points for pure Au clusters at 14 and 16 atoms, whereas pure Pd clusters are all found to be 3D. For Au-Pd nanoalloys, the role of cluster size and the influence of doping were found to be extensive and non-monotonic in altering cluster structures. Various stability criteria (e.g. binding energies, second differences in energy, and mixing energies) are used to evaluate the energetics, structures, and tendency of segregation in sub-nanometre Au-Pd clusters. HOMO-LUMO gaps were calculated to give additional information on cluster stability and a systematic homotop search was used to evaluate the energies of the generated global minima of monosubstituted clusters and the preferred doping sites, as well as confirming the validity of the BPGA-DFT approach.

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Section: Pd11contrasting

confidence: 84%

Section: Au Clusterssupporting

confidence: 64%

Section: Au Clustersmentioning

confidence: 66%

Section: Stabilitymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Application of a parallel genetic algorithm to the global optimization of medium-sized Au–Pd sub-nanometre clusters

2018

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Mining electronics waste: Experimental and computational mechanistic insights into organic aqua regia as an extraction method

Stuewe,

Nguyen,

Wei

et al. 2024

Applied Organom Chemis

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In the previous decade, organic aqua regia (OAR) was discovered as a mixture of pyridine and thionyl chloride that has been observed to surprisingly yet notably selectively dissolve precious metals, dissolution‐resistant gold. Given the novel combination is two common organic solvents, it has immense potential to contribute to a circular economy of metal recycling, economically and environmentally. The underlying mechanisms behind its metal dissolution and interesting properties are not well‐understood. Using both the original mixture and derivatives, the role of each OAR reagent was analyzed in the dissolution of gold to begin probing and illuminating the novel mechanism. Three mechanisms were proposed: radical based, oxidant and ligand, and Lewis acid and base. Computational means were used to propose possible mechanisms. Experiments were used to explicate the possible mechanisms. Discoveries from the original publication were used to verify assessments and suggest future areas of study for further confirmation. Based on the finding that 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) does not significantly affect the amount of gold dissolved, the radical mechanism was dismissed. Findings from experiments replacing pyridine with its derivatives disproved the likelihood of the oxidant and ligand mechanism. Finally, with the support of proton nuclear magnetic resonance (1H NMR) and other characterization techniques, the Lewis acid and base mechanism was determined to be the most probable mechanism of OAR. The mechanistic findings reported herein will pave the way for continued understanding of the mechanism to be exploited and optimized for other metals and organometallic chemistry in the recycling of metals.

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Non‐covalent Interactions and Charge Transfer between Propene and Neutral Yttrium‐Doped and Pure Gold Clusters

Barabás

Vanbuel

Ferrari

et al. 2019

Chemistry A European J

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The dopant and size‐dependent propene adsorption on neutral gold (Aun) and yttrium‐doped gold (Aun−1Y) clusters in the n=5–15 size range are investigated, combining mass spectrometry and gas phase reactions in a low‐pressure collision cell and density functional theory calculations. The adsorption energies, extracted from the experimental data using an RRKM analysis, show a similar size dependence as the quantum chemical results and are in the range of ≈0.6–1.2 eV. Yttrium doping significantly alters the propene adsorption energies for n=5, 12 and 13. Chemical bonding and energy decomposition analysis showed that there is no covalent bond between the cluster and propene, and that charge transfer and other non‐covalent interactions are dominant. The natural charges, Wiberg bond indices, and the importance of charge transfer all support an electron donation/back‐donation mechanism for the adsorption. Yttrium plays a significant role not only in the propene binding energy, but also in the chemical bonding in the cluster‐propene adduct. Propene preferentially binds to yttrium in small clusters (n<10), and to a gold atom at larger sizes. Besides charge transfer, relaxation also plays an important role, illustrating the non‐local effect of the yttrium dopant. It is shown that the frontier molecular orbitals of the clusters determine the chemical bonding, in line with the molecular‐like electronic structure of metal clusters.

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DFT global optimisation of gas-phase and MgO-supported sub-nanometre AuPd clusters

Cited by 41 publications

References 51 publications

Application of a parallel genetic algorithm to the global optimization of medium-sized Au–Pd sub-nanometre clusters

Application of a parallel genetic algorithm to the global optimization of medium-sized Au–Pd sub-nanometre clusters

Mining electronics waste: Experimental and computational mechanistic insights into organic aqua regia as an extraction method

Non‐covalent Interactions and Charge Transfer between Propene and Neutral Yttrium‐Doped and Pure Gold Clusters

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