Electronic subshell splitting controls the atomic structure of charged and neutral silver clusters

Gamboa, Gabriel U.; Reber, Arthur C.

doi:10.1039/c3nj01075a

Cited by 44 publications

(85 citation statements)

References 62 publications

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“…Compared to the results of Gamboa et al, 15 there are several different ground-state geometries of silver clusters, including neutral Ag 8-13 , anionic Ag 6,13 − and cationic Ag 6,10,11,13 + , for which we find slightly lower energy structures. These different structures obtained by us and Gamboa et al 15 may be raised by the complexity of the potential energy surfaces of the silver clusters.…”

Section: Resultscontrasting

confidence: 65%

“…15 Gamboa et al 15 considered the D 4d structure as the ground-state of Ag 10 (10b in Figure S1), however, our detailed calculation has found that it is 0.19 eV higher in energy than our D 2d symmetry structure. For neutral Ag 11 , the C 2 structure turns out to be the global minimum, 0.04 eV more stable than the C 2v structure (11c in Figure S1) of Gamboa et al.…”

Section: Resultsmentioning

confidence: 52%

“…Our findings point out that the ground-state neutral Ag 8 is of a high T d symmetry, 0.05 eV lower in energy than the C 2 structure (8b in Figure S1) of Gamboa et al. 15 The global minimum Ag 9…”

Section: Resultsmentioning

confidence: 58%

“…These different structures obtained by us and Gamboa et al 15 may be raised by the complexity of the potential energy surfaces of the silver clusters. Our findings point out that the ground-state neutral Ag 8 is of a high T d symmetry, 0.05 eV lower in energy than the C 2 structure (8b in Figure S1) of Gamboa et al.…”

Section: Resultsmentioning

confidence: 71%

“…A confined nearly free electron gas (NFEG) model, which is developed originally for alkali clusters, is usually used to rationalized the electronic behavior of silver clusters. [8][9][10][11][12][13][14][15][16] The spherical jellium model provides a simplified rule for realization of the shell character of clusters in which the valence electrons fill the spherical orbitals of a cluster according to the pattern of [1S 2 1P 6 1D 10 2S 2 1F 14 2P 6 1G 18 2D 10 …], where the uppercase letters are used to distinguish from the lowercase symbols labeled in atomic orbitals. [17][18][19][20][21][22][23][24] According to the spherical jellium model, clusters with fully filled electronic shells have large energy gaps between the highest occupied (HOMO) and lowest unoccupied molecular orbital (LUMO), and they are generally resistant to reactivity with small molecules.…”

Section: Introductionmentioning

confidence: 99%

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Ab Initio Search for Global Minimum Structures of Pure and Boron Doped Silver Clusters

et al. 2015

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The global minimum structures of pure and boron doped silver clusters up to 16 atoms are determined through ab initio calculations and unbiased structure searching methods. The structural and electronic properties of neutral, anionic, and cationic Ag(n)B (n ≤ 15) and Ag(n)B2 (n ≤ 14) clusters are much distinct from those of the corresponding pure silver. Considering that Ag and B possess one and three valence electrons, respectively, both the single and the double boron-atom doped silver clusters with even number of valence electrons are more stable than those with odd number of electrons, a feature also observed in the pure silver clusters. We demonstrate that the species with a valence count of 8 and 14 appear to be magic numbers with enhanced stability irrespective of component or the charged state. A new putative global minimum structure of Ag13(-) cluster, with high symmetry of C(2v), is unexpectedly observed as the ground state, which is lower in energy than the previous suggested bilayer structure.

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Section: Resultscontrasting

confidence: 65%

Section: Resultsmentioning

confidence: 52%

Section: Resultsmentioning

confidence: 58%

Section: Resultsmentioning

confidence: 71%

Section: Introductionmentioning

confidence: 99%

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Ab Initio Search for Global Minimum Structures of Pure and Boron Doped Silver Clusters

et al. 2015

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A Raman study on the intracluster interactions of aminothiophenol‐protected Ag₇ clusters—Photo‐assisted N─N coupling reaction of the ligand

Pan

Zhang

Yang

et al. 2020

J Raman Spectroscopy

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We have synthesized Ag 7 nanoclusters via a facile one-pot procedure with p-aminothiophenol (PATP) as the ligand. The chemical component of this Ag 7 cluster is determined to be Ag 7 (C 6 H 6 NS) 7 H + by high-resolution electrospray mass spectrometry, where a few fragment peaks are also observed such as [Ag 7 (C 6 H 6 NS) 4 H 3 Na] + . For this PATP-protected Ag 7 cluster, we have conducted a Raman investigation to probe in the intracluster interactions and find an essentially different Raman feature from that the nascent PATP ligand, pertaining to photo-assistant catalytic conversion of PATP to p,p'-dimercapto azobenzene (DMAB). Utilizing density-functional-theory (DFT) calculations, we have performed natural population analysis, natural bond orbital analysis, and electron density difference analysis to fully demonstrate the intracluster interactions between Ag 7 clusters and the ligand. What is interesting is that the protection ligand PATP helps stabilize the Ag 7 metallic core, and in turn, the metal core Ag 7 catalyzes the protection ligands giving rise to N─N coupling reaction. On this basis, we have proposed a reaction pathway on a basis of DFT calculations to provide further insights into the reaction mechanism of PATP-to-DMAB conversion at the presence of the Ag 7 clusters.

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Structural, Energetic, and Magnetic Properties of Ag $$_{n-m}$$ n - m Rh $$_{m}$$ m and Ag $$_{m}$$ m Rh $$_{n-m}$$ n - m Clusters with $$n \le 20$$ n ≤ 20 and $$m=0,1$$ m = 0 , 1

Kohaut

Springborg

2016

J Clust Sci

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Electronic subshell splitting controls the atomic structure of charged and neutral silver clusters

Cited by 44 publications

References 62 publications

Ab Initio Search for Global Minimum Structures of Pure and Boron Doped Silver Clusters

Ab Initio Search for Global Minimum Structures of Pure and Boron Doped Silver Clusters

A Raman study on the intracluster interactions of aminothiophenol‐protected Ag₇ clusters—Photo‐assisted N─N coupling reaction of the ligand

Structural, Energetic, and Magnetic Properties of Ag $$_{n-m}$$ n - m Rh $$_{m}$$ m and Ag $$_{m}$$ m Rh $$_{n-m}$$ n - m Clusters with $$n \le 20$$ n ≤ 20 and $$m=0,1$$ m = 0 , 1

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Electronic subshell splitting controls the atomic structure of charged and neutral silver clusters

Cited by 44 publications

References 62 publications

Ab Initio Search for Global Minimum Structures of Pure and Boron Doped Silver Clusters

Ab Initio Search for Global Minimum Structures of Pure and Boron Doped Silver Clusters

A Raman study on the intracluster interactions of aminothiophenol‐protected Ag7 clusters—Photo‐assisted N─N coupling reaction of the ligand

Structural, Energetic, and Magnetic Properties of Ag $$_{n-m}$$ n - m Rh $$_{m}$$ m and Ag $$_{m}$$ m Rh $$_{n-m}$$ n - m Clusters with $$n \le 20$$ n ≤ 20 and $$m=0,1$$ m = 0 , 1

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A Raman study on the intracluster interactions of aminothiophenol‐protected Ag₇ clusters—Photo‐assisted N─N coupling reaction of the ligand