Delocalized electronic states in small clusters. Comparison of Nan, Cun, Agn, and Aun clusters

Handschuh, H.; Cha, Chia-Yen; Möller, H.; Bechthold, P. S.; Ganteför, Gerd; Eberhardt, W.

doi:10.1016/0009-2614(94)00836-1

Cited by 35 publications

(25 citation statements)

References 14 publications

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“…67,68 That T d (fcc) structure was proposed earlier by Koutecký et al 69 as one of the two low-energy forms of Li 20 resulting from an effective core potential calculation including core-valence correlations. However, an analysis of the electronic and geometrical structure of sodium and coinage metal clusters, based on photoelectron spectra of anionic clusters containing up to 20 atoms, 70,71 indicates that the electronic structures of Ag and Cu clusters are similar to those of Na clusters, whereas the photoelectron spectra of gold clusters display many more features and fine structure than those of copper and silver.…”

Section: Anionmentioning

confidence: 96%

Trends in the structure and bonding of noble metal clusters

et al. 2004

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We present a systematic study of the electronic properties and the geometric structure of noble metal clusters X n (X = Cu, Ag, Au; =−1,0, +1; n ഛ 13 and n =20), obtained from first-principles generalized gradient approximation density functional calculations based on norm-conserving pseudopotentials and numerical atomic basis sets. We obtain planar structures for the ground state of anionic ͑ =−1͒, neutral ͑ =0͒, and cationic ͑ =1͒ species of gold clusters with up to 12, 11, and 7 atoms, respectively. In contrast, the maximum size of planar clusters with =−1,0, +1 are n = ͑5,6,5͒ for silver and (5,6,4) for copper. For X 20 we find a T d symmetry for gold and a compact C s structure for silver and copper. Our results for the cluster geometries agree partially with previous first-principles calculations, and they are in good agreement with recent experimental results for anionic and cationic gold clusters. The tendency to planarity of gold clusters, which is much larger than in copper and silver, is strongly favored by relativistic effects, which decrease the s-d promotion energy and lead to hybridization of the half-filled 6s orbital with the fully occupied 5d z 2 orbital. That picture is substantiated by analyzing our calculated density matrix for planar and three-dimensional clusters of gold and copper. The trends for the cohesive energy, ionization potentials, electron affinities, and highest accupied and lowest unoccupied molecular orbital gap, as the cluster size increases, are studied in detail for each noble metal and rationalized in terms of two-and three-dimensional electronic shell models. The most probable fragmentation channels for X n clusters are in very good agreement with available experiments.

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Section: Anionmentioning

confidence: 96%

Trends in the structure and bonding of noble metal clusters

et al. 2004

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“…Ganteför and coworkers studied clusters of metals with n ϭ 2-20 atoms (in particular, Na n Ϫ , Cu n Ϫ , Ag n Ϫ , and Au n Ϫ ), with an energy resolution sufficient to reveal details of the neutral electronic structure (Handschuh et al, 1994a). The anions are generated either in a laser vaporization source (Ag, Au) or in a pulsed arc cluster ion source (Na, Cu).…”

Section: B Metal and Semiconductor Clustersmentioning

confidence: 99%

Negative ions, mass selection, and photoelectrons

Boesl

Knott

1998

Mass Spectrom. Rev.

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“…Au clusters exhibit the most pronounced even-odd alternation of the electronic structure of any cluster with the change in the electron affinity (EA) between Au 2 and Au 3 being more than 1.5 eV. [5] Au 6 , Au 8 and Au 20 have large HOMO-LUMO (H-L) gaps making them stable and therefore possibly suitable as building blocks for new materials. The interaction of Au n clusters with O 2 studied using anion photoelectron spectroscopy and density functional calculations show that the geometric and electronic structures are altered considerably by this interaction, although the O 2 molecule is not bound strongly.…”

Section: Introductionmentioning

confidence: 99%

Origin of the Unusual Properties of Au_n(BO₂) Clusters

et al. 2010

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We report the discovery of a new class of clusters consisting of Au(n)(BO(2)) that forms during the oxygenation of gold clusters when boron nitride is used as insulation in a pulsed-arc cluster ion source (PACIS). Photoelectron and mass spectroscopy of these clusters further revealed some remarkable properties: instead of the expected Au(n)O(m) peaks, the mass spectra contain intense peaks corresponding to Au(n)(BO(2)) composition. Some of the most predominant features of the electronic structure of the bare Au clusters, namely even-odd alternation in the electron affinity, are preserved in the Au(n)(BO(2)) species. Most importantly, Au(n)(BO(2)) [odd n] clusters possess unusually large electron affinity values for a closed-shell cluster, ranging from 2.8-3.5 eV. The open-shell Au(n)(BO(2)) [even n] clusters on the other hand, possess electron affinities exceeding that of F, the most electronegative element in the periodic table. Using calculations based on density functional theory, we trace the origin of these species to the unusual stability and high electron affinity of the BO(2) moiety. The resulting bond formed between BO(2) and Au(n) clusters preserves the geometric and electronic structure of the bare Au(n) clusters. The large electron affinity of these clusters is due to the delocalization of the extra electron over the Au(n) cluster.

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Delocalized electronic states in small clusters. Comparison of Nan, Cun, Agn, and Aun clusters

Cited by 35 publications

References 14 publications

Trends in the structure and bonding of noble metal clusters

Trends in the structure and bonding of noble metal clusters

Negative ions, mass selection, and photoelectrons

Origin of the Unusual Properties of Au_n(BO₂) Clusters

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Delocalized electronic states in small clusters. Comparison of Nan, Cun, Agn, and Aun clusters

Cited by 35 publications

References 14 publications

Trends in the structure and bonding of noble metal clusters

Trends in the structure and bonding of noble metal clusters

Negative ions, mass selection, and photoelectrons

Origin of the Unusual Properties of Aun(BO2) Clusters

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Origin of the Unusual Properties of Au_n(BO₂) Clusters