Electronic structure analysis of small gold clusters Au m (m ≤ 16) by density functional theory

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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“…Geometries of the most stable Au n clusters are taken from ref. . For Au n −1 Y with n= 5–10, the geometries were adapted from ref.…”

Section: Methodsmentioning

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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“…Among the metal clusters, there is an increasing interest [20][21][22][23][24][25][26][27][28][29][30][31][32] in the noble metals (Cu, Ag, and Au) because they can be considered as a connection between the alkali metals and the transition metals. We recall that their electronic configurations are nd 10 (n + 1)s 1 , with n = 3, 4, and 5, respectively to Cu, Ag and Au.…”

Section: Introductionmentioning

confidence: 99%

“…As the central processing unit (CPU) time enhances rapidly with the cluster size, effective core potential (ECP) with a valence basis set has been extensively used to overcome difficulties. 27,[29][30][31][32] Another alternative is to employ relativistic density functional theory (DFT) along with an accurate allelectron basis set. To our knowledge, for the gold clusters, the latter strategy has not been used so far.…”

mentioning

confidence: 99%

Structures, Stabilities, Reactivities, and (Hyper)Polarizabilities of Small Gold Clusters

Jorge¹,

Santos²

2017

J. Braz. Chem. Soc.

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At the Douglas-Kroll-Hess level, the B3PW91 hybrid functional along with relativistic all-electron basis sets are used to evaluate geometric parameters, binding energies, vertical ionization potentials and electron affinities, and HOMO-LUMO (highest occupied molecular orbital-lowest unoccupied molecular orbital) energy gaps of the small golden clusters (Au n , n ≤ 8).The so expected odd-even oscillations of the experimental ionization potentials and electron affinities are confirmed in this work and the Au 7 cluster is predicted to be the most reactive cluster. Using the optimized geometries, DKH2 static mean dipole polarizability and polarizability anisotropy are also computed. From n ≥ 2, the mean dipole polarizabilities per atom present an odd-even oscillatory characteristic, whereas the polarizability anisotropies increase with the cluster size. At the non-relativistic level, the second hyperpolarizabilities are calculated. It is the first time that hyperpolarizabilities of gold clusters are reported. Comparisons with theoretical results obtained previously for the copper and silver clusters at the same level of theory are made.Keywords: B3PW91 functional, all-electron basis sets, DKH2 calculations, gold clusters, (hyper)polarizabilities IntroductionAtomic cluster is formed by an assembling of a few or hundreds of atoms. It is necessary to understand how the cluster properties vary with the size, to clarify how they evolve in the direction of the bulk properties. Metal clusters have received special attention in the literature due to their unusual characteristics, properties, and applications to build new electronic devices.1 Theoretical 2-11 and experimental [12][13][14][15][16][17][18][19] studies about metal clusters have been carried out for about thirty three years. Among the metal clusters, there is an increasing interest [20][21][22][23][24][25][26][27][28][29][30][31][32] in the noble metals (Cu, Ag, and Au) because they can be considered as a connection between the alkali metals and the transition metals. We recall that their electronic configurations are nd 10 (n + 1)s 1 , with n = 3, 4, and 5, respectively to Cu, Ag and Au. It has been verified that in general the gold clusters and compounds present large relativistic effects when compared to those of the copper and silver ones. 33,34 We would like to cite the experiments about vertical ionization potentials and electron affinities performed by some research groups, 28,[35][36][37][38][39] where the results of all studied gold clusters surpass those of the copper and silver ones (see Figure 2 of Wesendrup et al.). 29 As a consequence of this finding, the properties and surfaces of the gold clusters will be differently affected. Thus, a study about the variation of such properties with the cluster size will be interesting. In this article, the vertical ionization potentials and electron affinities of gold clusters with up to 8 atoms as well as binding energies, highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) energ...

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“…Gold clusters and nanoparticles have attracted continuous attention for their important electronic, catalytic, and optical properties [1][2][3][4]. With the reactivity increasing as the particle diameter decreasing, the catalytic activity of gold clusters depends on particle size, which is one of the key parameters determining the unexpected catalytic activity of gold [5].…”

Section: Introductionmentioning

confidence: 99%

“…In a recent report, the transition from 2D to 3D structures in small gold clusters occurred around 10 atoms by density functional and wavefunction-based methods [6]. Small gold clusters Au n (n B 16) were analyzed using the density functional theory (DFT) at B3LYP level with a Lanl2DZ pseudopotential to understand the rules governing the structures obtained for the most stable clusters [2]. The transition from flat-cage (Au 15 and Au 16 ) to hollow-cage structure (Au 17 and Au 18 ) was found at Au 17 , and the variation from hollow-cage to pyramidal structure was recognized at Au 19 [7,8].…”

Section: Introductionmentioning

confidence: 99%

Geometrical structures and energetics of gold clusters from Au13 to Au300

Dong

2014

Struct Chem

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The growth pattern of gold clusters containing up to 300 atoms was studied. The interatomic interaction is modeled by Gupta potential with density-functional-theory-fitted parameters. The stable structures of Au 13-300 clusters are obtained by dynamic lattice searching (DLS) and DLS with constructed cores (DLSc) methods. In the optimized structures of Au 13-88 clusters, most of clusters adopt the decahedral motifs, except for twelve face-centered cubic (FCC) and stacking fault (SF) FCC motifs. With respect to the wide appearance of the three kinds of motifs, corresponding inner cores are constructed in the DLSc method to optimize Au 90-300 clusters with several tens number of atoms. Results show that the major motifs are FCC and SF FCC, except for decahedra at Au 110 , Au 160 , Au 180 , Au 190 , and Au 230 . Furthermore, the ratio of SF FCC structures is obviously increasing, it can, thus, be deduced that SF FCC motif is more stable in large size gold clusters.

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Electronic structure analysis of small gold clusters Au m (m ≤ 16) by density functional theory

Cited by 37 publications

References 40 publications

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

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

Structures, Stabilities, Reactivities, and (Hyper)Polarizabilities of Small Gold Clusters

Geometrical structures and energetics of gold clusters from Au13 to Au300

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