Transition from exohedral to endohedral structures of AuGe<sub>n</sub><sup>−</sup> (n = 2–12) clusters: photoelectron spectroscopy and ab initio calculations

Lu, Sheng-Jie; Hu, Lianrui; Xu, Xi-Ling; Xu, Hong‐Guang; Chen, Hui; Zheng, Wei‐Jun

doi:10.1039/c6cp00373g

Cited by 53 publications

(53 citation statements)

References 67 publications

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“…To the best of our knowledge, that has never been reported previously. And it is in line with the recent photoelectron spectroscopy results on small AuGenwhich has suggested strong interactions between the 5d orbitals of the Au atom and the 4s4p hybridized orbitals of the Ge atoms 25 .…”

Section: Discussionsupporting

confidence: 90%

“…The isoelectronic cluster RuGe12 3is also found to lie in the D2h structure 50 . Previous works on the anion AuGe12have furnished conflicting results since Li et al 24 has predicted a D2d structure to be the lowest-isomer with hybrid DFT + MP2 level calculations, while Lu et al 25 obtained a Ih-symmetry structure using DFT + CCSD calculations. The latter is in better agreement with the photoelectron spectroscopy results 25 .…”

Section: Results 3a Structural Propertiesmentioning

confidence: 99%

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Growth Behavior and Electronic Structure of Noble Metal-Doped Germanium Clusters

2018

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Structures, energetics, and electronic properties of noble metal-doped germanium (MGe with M = Cu, Ag, Au; n = 1-19) clusters are systematically investigated by using the density functional theory (DFT) approach. The endohedral structures in which the metal atom is encapsulated inside of a germanium cage appear at n = 10 when the dopant is Cu and n = 12 for M = Ag and Au. While Cu doping enhances the stability of the corresponding germanium frame, the binding energies of AgGe and AuGe are always lower than those of pure germanium clusters. Our results highlight the great stability of the CuGe cluster in a D structure and, to a lesser extent, that of AgGe and AuGe, which exhibits a hollow cage-like geometry. The sphere-type geometries obtained for n = 10-15 present a peculiar electronic structure in which the valence electrons of the noble metal and Ge atoms are delocalized and exhibit a shell structure associated with the quasi-spherical geometry. It is found that the coinage metal is able to give both s- and d-type electrons to be reorganized together with the valence electrons of Ge atoms through a pooling of electrons. The cluster size dependence of the stability, the frontier orbital energy gap, the vertical ionization potentials, and electron affinities are given.

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Section: Discussionsupporting

confidence: 90%

Section: Results 3a Structural Propertiesmentioning

confidence: 99%

Growth Behavior and Electronic Structure of Noble Metal-Doped Germanium Clusters

2018

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“…28 Interestingly, our photoelectron experimental data show that the BSi 9 − cluster has a large VDE of 3.9 eV, which is slightly higher than the electronic affinities (EAs) of the Cl atom (3.61 eV) 61 and Al 13 (3.57 eV). 62 Thus, BSi 9 − can be viewed as a superhalogen anion, similar to Al 13 − and AuGe 12 − , 63,64 and may have potential applications as building blocks for novel nanostructured materials. 65 Our calculations found that the most stable structure of neutral BSi 9 is an endohedral structure with the B atom at the center, different from that of BSi 9 − .…”

Section: Bsi 12mentioning

confidence: 99%

Structural evolution and bonding properties of BSin−/ (n = 4–12) clusters: Size-selected anion photoelectron spectroscopy and theoretical calculations

Cao

et al. 2018

The Journal of Chemical Physics

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Size-selected anion photoelectron spectroscopy and theoretical calculations were used to investigate the structural evolution and bonding properties of BSi n −/0 (n = 4-12) clusters. The results showed that the B atom in BSi 4-12 −/0 prefers to occupy the high coordination sites to form more B-Si bonds. The lowest-lying isomers of BSi 4-7 −/0 primarily adopt bowl-shaped based geometries, while those of BSi 8-12 −/0 are mainly dominated by prismatic based geometries. For anionic clusters, BSi 11 − is the critical size of the endohedral structure, whereas BSi n neutrals form the B-endohedral structure at n = 9. Interestingly, both anionic and neutral BSi 11 have a D 3h symmetric tricapped tetragonal antiprism structure with the B atom at the center and exhibit 3D aromaticity. The BSi 11 − anion possesses σ plus π doubly delocalized bonding characters. The natural population analysis charge distributions on the B atom are related with the structural evolution of BSi n − and the B-Si interactions.

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“…In the calculations, the singlet and triplet spin states were examined for each initial structure, and the zero-point vibrational correction was included into the relative energies. According to the previous works on the neutral [ 24 ] and cationic [ 39 ] Ge n Au clusters, we searched a large number of initial isomers for the alkali metals-adsorbed gold-doped germanium clusters from the following steps. One is that the alkali metal atoms are attached to different germanium positions on the surface, edge or apex of the lowest-energy structures of the Ge n Au clusters.…”

Section: Computational Detailsmentioning

confidence: 99%

Effect of Alkali Metal Atoms Doping on Structural and Nonlinear Optical Properties of the Gold-Germanium Bimetallic Clusters

Ren

et al. 2017

Nanomaterials

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A new series of alkali-based complexes, AM@GenAu (AM = Li, Na, and K), have been theoretically designed and investigated by means of the density functional theory calculations. The geometric structures and electronic properties of the species are systematically analyzed. The adsorption of alkali metals maintains the structural framework of the gold-germanium bimetallic clusters, and the alkali metals prefer energetically to be attached on clusters’ surfaces or edges. The high chemical stability of Li@Ge12Au is revealed by the spherical aromaticity, the hybridization between the Ge atoms and Au-4d states, and delocalized multi-center bonds, as well as large binding energies. The static first hyperpolarizability (βtot) is related to the cluster size and geometric structure, and the AM@GenAu (AM = Na and K) clusters exhibit the much larger βtot values up to 13050 a.u., which are considerable to establish their strong nonlinear optical (NLO) behaviors. We hope that this study will promote further application of alkali metals-adsorbed germanium-based semiconductor materials, serving for the design of remarkable and tunable NLO materials.

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Transition from exohedral to endohedral structures of AuGe_n⁻ (n = 2–12) clusters: photoelectron spectroscopy and ab initio calculations

Cited by 53 publications

References 67 publications

Growth Behavior and Electronic Structure of Noble Metal-Doped Germanium Clusters

Growth Behavior and Electronic Structure of Noble Metal-Doped Germanium Clusters

Structural evolution and bonding properties of BSin−/ (n = 4–12) clusters: Size-selected anion photoelectron spectroscopy and theoretical calculations

Effect of Alkali Metal Atoms Doping on Structural and Nonlinear Optical Properties of the Gold-Germanium Bimetallic Clusters

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Transition from exohedral to endohedral structures of AuGen− (n = 2–12) clusters: photoelectron spectroscopy and ab initio calculations

Cited by 53 publications

References 67 publications

Growth Behavior and Electronic Structure of Noble Metal-Doped Germanium Clusters

Growth Behavior and Electronic Structure of Noble Metal-Doped Germanium Clusters

Structural evolution and bonding properties of BSin−/ (n = 4–12) clusters: Size-selected anion photoelectron spectroscopy and theoretical calculations

Effect of Alkali Metal Atoms Doping on Structural and Nonlinear Optical Properties of the Gold-Germanium Bimetallic Clusters

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Transition from exohedral to endohedral structures of AuGe_n⁻ (n = 2–12) clusters: photoelectron spectroscopy and ab initio calculations