Analysis of the bonding and reactivity of H and the Al13 cluster using density functional concepts

Mañanes, Á.; Duque, F.; Méndez, Francisco; López, M. J.; Alonso, J. A.

doi:10.1063/1.1597673

Cited by 56 publications

(70 citation statements)

References 58 publications

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“…In particular, the electronic charge forms a framework throughout the cluster with the highest densities located in the interstitial regions. This corresponds with development of metallic or Jelliumlike bonding and compares well with earlier studies of Al 13 , Al 13 -and Al 12 Si [39][40][41][42][43]. As reported previously this is also evidenced by the high degree of degeneracy in the eigenvalue spectrum of endo-Ga 12 C [19,44].…”

Section: Resultssupporting

confidence: 76%

Bonding in doped gallium nanoclusters: Insights from regional DFT

Henry

Ichikawa

Nozaki

et al. 2016

Computational Materials Science

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Abstract:The molecular nature (Ga 2 ) n of gallium makes this an interesting metal to investigate for the development of novel nano-materials. However, establishment of a targeted approach to manipulating the properties of gallium clusters requires a detailed understanding of how doping affects the bonding in these species. In this study, the bonding of gallium nanoclusters has been investigated using electron deformation densities and Regional Density Functional Theory (RDFT). Bonding throughout Ga 12 X clusters is generally intermediate between covalent and metallic. However, the presence of Ga 2 subunits is clearly identified in clusters with endohedral dopants (Ga 12 X, X = Al, Si, P, Ga, Ge, As).Although there is evidence of Ga 2 subunits in exohedral doped clusters, localized bonding to the dopant generally leads to significant disruption to the cluster framework. Maps of electronic chemical potential provide understanding for the observed differences in regioselectivity for hydrogen adsorption.

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Section: Resultssupporting

confidence: 76%

Bonding in doped gallium nanoclusters: Insights from regional DFT

Henry

Ichikawa

Nozaki

et al. 2016

Computational Materials Science

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“…Experimental studies suggest that Al 13 -is highly symmetric 2 and cannot be etched by oxygen. 3 These properties are in agreement with its description as a "magic cluster" according to the jellium model, 4 in which the nuclear geometry of the cluster is approximated as a spherical charge distribution interacting with delocalized valence electrons.…”

Section: ' Introductionmentioning

confidence: 99%

“…1 Therefore, Al 13 -is of potential interest as an anion in ionic liquids. Experimental studies suggest that Al 13 -is highly symmetric 2 and cannot be etched by oxygen.…”

Section: ' Introductionmentioning

confidence: 99%

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Electron Affinity of Al₁₃: A Correlated Electronic Structure Study

Smith

Gordon

2011

J. Phys. Chem. A

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Neutral and anionic 13-atom aluminum clusters are studied with high-level, fully ab initio methods: secondorder perturbation theory (MP2) and coupled cluster theory with singles, doubles, and perturbative triples (CCSD(T)). Energies and vibrational frequencies are reported for icosahedral and decahedral isomers, and are compared with density functional theory results. At the MP2 level of theory, with all of the basis sets employed, the icosahedral structure is energetically favored over the decahedral structure for both the neutral and anionic Al13 clusters. Hessian calculations imply that only the icosahedral structures are potential energy minima. The CCSD(T)/aug-cc-pVTZ adiabatic electron affinity of Al13 is found to be 3.57 eV, in excellent agreement with experiment. ABSTRACT: Neutral and anionic 13-atom aluminum clusters are studied with high-level, fully ab initio methods: second-order perturbation theory (MP2) and coupled cluster theory with singles, doubles, and perturbative triples (CCSD(T)). Energies and vibrational frequencies are reported for icosahedral and decahedral isomers, and are compared with density functional theory results. At the MP2 level of theory, with all of the basis sets employed, the icosahedral structure is energetically favored over the decahedral structure for both the neutral and anionic Al 13 clusters. Hessian calculations imply that only the icosahedral structures are potential energy minima. The CCSD(T)/ aug-cc-pVTZ adiabatic electron affinity of Al 13 is found to be 3.57 eV, in excellent agreement with experiment.

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“…A controversy has arisen regarding the correct global minimum ͑GM͒ for Al 13 : the optimizations based on parametrized potential models 32,34,35,41,42,46,52 invariably predict an icosahedral structure, but these methods do not contain an explicit description of the electronic degrees of freedom and their accuracy is questionable. A majority of the ab initio calculations ͓mostly based on density functional theory ͑DFT͒ and differing in the election of exchangecorrelation functional, aluminum pseudopotential, and basis set͔ predict an icosahedron as the most stable structure, [22][23][24][25]27,28,30,33,37,39,45 but a small number of calculations 26,31,38,48,49 predict a decahedron to be more stable. In some cases the energy difference between icosahedral and decahedral structures is very small and therefore below the expected accuracy of DFT methods.…”

Section: Introductionmentioning

confidence: 99%

Structures and stabilities of Aln+, Aln, and Aln− (n=13–34) clusters

Aguado

López

2009

The Journal of Chemical Physics

100

105

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Putative global minima of neutral ͑Al n ͒ and singly charged ͑Al n + and Al n − ͒ aluminum clusters with n = 13-34 have been located from first-principles density functional theory structural optimizations. The calculations include spin polarization and employ the generalized gradient approximation of Perdew, Burke, and Ernzerhof to describe exchange-correlation electronic effects. Our results show that icosahedral growth dominates the structures of aluminum clusters for n = 13-22. For n = 23-34, there is a strong competition between decahedral structures, relaxed fragments of a fcc crystalline lattice ͑some of them including stacking faults͒, and hexagonal prismatic structures. For such small cluster sizes, there is no evidence yet for a clear establishment of the fcc atomic packing prevalent in bulk aluminum. The global minimum structure for a given number of atoms depends significantly on the cluster charge for most cluster sizes. An explicit comparison is made with previous theoretical results in the range n = 13-30: for n = 19, 22, 24, 25, 26, 29, 30 we locate a lower energy structure than previously reported. Sizes n = 32, 33 are studied here for the first time by an ab initio technique.

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Analysis of the bonding and reactivity of H and the Al13 cluster using density functional concepts

Cited by 56 publications

References 58 publications

Bonding in doped gallium nanoclusters: Insights from regional DFT

Bonding in doped gallium nanoclusters: Insights from regional DFT

Electron Affinity of Al₁₃: A Correlated Electronic Structure Study

Structures and stabilities of Aln+, Aln, and Aln− (n=13–34) clusters

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Analysis of the bonding and reactivity of H and the Al13 cluster using density functional concepts

Cited by 56 publications

References 58 publications

Bonding in doped gallium nanoclusters: Insights from regional DFT

Bonding in doped gallium nanoclusters: Insights from regional DFT

Electron Affinity of Al13: A Correlated Electronic Structure Study

Structures and stabilities of Aln+, Aln, and Aln− (n=13–34) clusters

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Product

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Electron Affinity of Al₁₃: A Correlated Electronic Structure Study