Structures and Stabilities of the Metal Doped Gold Nano-Clusters: M@Au10 (M = W, Mo, Ru, Co)

Hossain, Delwar; Pittman, Charles U.; Gwaltney, Steven R.

doi:10.1007/s10904-013-9995-6

Cited by 11 publications

(8 citation statements)

References 48 publications

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“…As for the smaller-sized M@Au n clusters with n < 12, Hossain et al 687 extended the scope of M@Au n cage clusters down to n = 10 with endohedral bicapped tetragonal antiprism or prism structure and related distorted cage configurations, or a pentagonal antiprism structure using LanL2DZ basis set and different exchange-correlation functionals. They found that an M atom (M = W, Mo, Ru, Co) can be encapsulated in Au 10 cage with appreciable binding energies and moderate HOMO−LUMO gaps.…”

Section: Doped Au Cagesmentioning

confidence: 99%

Endohedrally Doped Cage Clusters

2020

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The discovery of carbon fullerene cages and their solids opened a new avenue to build materials from stable cage clusters as “artificial atoms” or “superatoms” instead of atoms. However, cage clusters of other elements are generally not stable. In 2001, ab initio calculations showed that endohedral doping of Zr and Ti atoms leads to highly stable Zr@Si16 fullerene and Ti@Si16 Frank–Kasper polyhedral clusters with large HOMO–LUMO gaps. In 2002, Zr@Ge16 was shown to form a Frank–Kasper polyhedron, suggesting the possibility of designing novel clusters by tuning endohedral and cage atoms. These results were subsequently confirmed from experiments. In the past nearly two decades, many experimental and theoretical studies have been carried out on different clusters, and many very stable cage clusters with possibly high abundance have been found by endohedral doping. Indeed in 2017, Ta@Si16 and Ti@Si16 cage clusters have been synthesized in bulk quantity of about 100 mg using a dry-chemistry method, giving rise to a new hope of developing cluster-based materials in macroscopic quantity besides the well-known C60 fullerene solid. Also, wet-chemistry methods have been used to synthesize endohedrally doped clusters as well as ligated clusters and their solids, which auger well for the development of novel nanostructured materials using atomically precise clusters with unique properties. In this comprehensive review, we present results of many such developments in this fast-growing field including (i) endohedrally doped Al, Ga, and In clusters, (ii) small endohedral carbon fullerene cages with ≤ 28 carbon atoms, (iii) metal doped boron cages, (iv) endohedrally doped cages of group 14 elements (Si, Ge, Sn, and Pb), (v) coinage metal (Cu, Ag, Au) cages doped with a transition metal atom as well as their ligated clusters and crystals, (vi) endohedrally doped cages of compound semiconductors, and (vii) multilayer Matryoshka cages and core–shell structures. In a large number of cases, we have performed ab initio calculations to present updated results of the most stable atomic structures and fundamental electronic properties of the endohedrally doped cage clusters. We discuss electronic, magnetic, optical, and catalytic properties in order to shed light on their potential applications. The stability of the doped cage clusters has been correlated to the concept of filling the electronic shells for superatoms such as within a spherical potential model and also using various electron counting rules including Wade–Mingos rules, systems with 18 and 32 electrons, and the spherical aromaticity rule. We also discuss cluster–cluster interaction in cluster dimers and assemblies of some of the promising doped cage clusters in different dimensions. Finally, we give a perspective of this field with a bright future.

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Section: Doped Au Cagesmentioning

confidence: 99%

Endohedrally Doped Cage Clusters

2020

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“…The electronic and geometric properties of gold clusters can be tuned by the introduction of a dopant atom, which also influences the chemical properties of the clusters. For example, the binding energies, as well as the HOMO–LUMO gaps, were found to be enhanced by Mo, Ru, and Co doping . Pd doping also substantially alters the stability patterns of cationic gold clusters .…”

Section: Introductionmentioning

confidence: 99%

“…For example, the binding energies, as well as the HOMO-LUMO gaps, were found to be enhancedb yM o, Ru, and Co doping. [15] Pd dopinga lso substantially alters the stability patterns of cationic gold clusters. [16] Doping of both neutrala nd cationic gold clusters with as ilver atom reduces their reactivityt owards CO, [17,18] while doping neutralg old clusters with vanadium decreases their reactivity towardsC Oi nt he size range of 14 to 20 atoms.…”

Section: Introductionmentioning

confidence: 99%

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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“…They are shown in Figure . The stability of these BP86 results is supported by different comparison of GGA and GGA‐Hybrid methods on the calculation of gold cluster properties . The structure of [WAu 12 ] ( n = 0) is also shown for comparison.…”

Section: Resultsmentioning

confidence: 76%

Symmetry lowering by cage doping in spherical superatoms: Evaluation of electronic and optical properties of 18‐electron W@Au₁₂Pt_n (n = 0‐4) superatomic clusters from relativistic DFT calculations

Gam

Arratia‐Pérez

Kahlal

et al. 2018

Int J of Quantum Chemistry

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Attempts to expand the versatility of well defined clusters are a relevant issue in the design of building blocks for functional nanostructures. Here, we investigate the plausible formation of related structures from the emblematic highly symmetrical 18‐e [W@Au12] cluster. The calculated [W@Au12Ptn] series, with n = 0, 1, 2, 3, and 4, show cohesion energies, HOMO‐LUMO gap, adiabatic electron affinities (AEAs) and adiabatic ionization potentials (AIPs), indicating a relative stability to the parent cluster [W@Au12] experimentally characterized, where clusters with n = 1 and n = 4 are suggested as the most stable with respect to oxidation. The resulting symmetry lowering away from the high icosahedral symmetry upon adding Pt atoms induces a sizable splitting of the frontiers shells, which in turn effectively modify the properties of the calculated clusters, as observed from calculated optical properties. The estimated absorption spectra show an interesting broadening effect of the absorption peaks, which appears as a useful approach for further design of broad black absorbers, which are able to absorb light in a wider range, with potential capabilities to enhance the efficiency of thin film solar cells and photocatalysis processes, among other applications.

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Structures and Stabilities of the Metal Doped Gold Nano-Clusters: M@Au10 (M = W, Mo, Ru, Co)

Cited by 11 publications

References 48 publications

Endohedrally Doped Cage Clusters

Endohedrally Doped Cage Clusters

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

Symmetry lowering by cage doping in spherical superatoms: Evaluation of electronic and optical properties of 18‐electron W@Au₁₂Pt_n (n = 0‐4) superatomic clusters from relativistic DFT calculations

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Structures and Stabilities of the Metal Doped Gold Nano-Clusters: M@Au10 (M = W, Mo, Ru, Co)

Cited by 11 publications

References 48 publications

Endohedrally Doped Cage Clusters

Endohedrally Doped Cage Clusters

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

Symmetry lowering by cage doping in spherical superatoms: Evaluation of electronic and optical properties of 18‐electron W@Au12Ptn (n = 0‐4) superatomic clusters from relativistic DFT calculations

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Symmetry lowering by cage doping in spherical superatoms: Evaluation of electronic and optical properties of 18‐electron W@Au₁₂Pt_n (n = 0‐4) superatomic clusters from relativistic DFT calculations