Charge Transfer Complexation of Ta-Encapsulating Ta@Si<sub>16</sub> Superatom with C<sub>60</sub>

Ohta, Tsutomu; Shibuta, Masahiro; Tsunoyama, Hironori; Eguchi, Toyoaki; Nakajima, Atsushi

doi:10.1021/acs.jpcc.6b04955

Cited by 34 publications

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References 55 publications

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“…In this respect, it is worth mentioning the transition metal (M) encapsulating silicon super atoms, M@Si 16 , which have been probed in the gas‐phase molecular beam, and predicted by quantum chemical calculations, but not yet isolated [51] . However, the structure of surface‐immobilized M@Si 16 clusters has been elucidated using scanning probe microscopy and photoelectron spectroscopy, glimpsing a way toward future functional materials in the solid state [51–53] …”

Section: Figurementioning

confidence: 99%

Li₈Si₈, Li₁₀Si₉, and Li₁₂Si₁₀: Assemblies of Lithium‐Silicon Aromatic Units

et al. 2021

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We report the global minima structures of Li8Si8, Li10Si9, and Li12Si10 systems, in which silicon moieties maintain structural and chemical bonding characteristics similar to those of their building blocks: the aromatic clusters Td−Li4Si4 and C2v−Li6Si5. Electron counting rules, chemical bonding analysis, and magnetic response properties verify the silicon unit‘s aromaticity persistence. This study demonstrates the feasibility of assembling silicon‐based nanostructures from aromatics clusters as building blocks.

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Section: Figurementioning

confidence: 99%

Li₈Si₈, Li₁₀Si₉, and Li₁₂Si₁₀: Assemblies of Lithium‐Silicon Aromatic Units

et al. 2021

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“…Single-size nanocluster ions are deposited on a solid substrate with a typical kinetic energy of 5–30 eV (<1 eV/atom) by adjusting the bias voltage applied to the substrate. Since the kinetic energy distribution of nanocluster ions is narrow enough, they can be immobilized on the substrate without fragmentation. − …”

Section: Fabrication Of Surface Immobilized and Ligand-stabilized Sup...mentioning

confidence: 99%

Section: Fabrication Of Surface Immobilized and Ligand-stabilized Sup...mentioning

confidence: 99%

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Synthesis and Characterization of Metal-Encapsulating Si₁₆ Cage Superatoms

et al. 2018

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Nanoclusters, aggregates of several to hundreds of atoms, have been one of the central issues of nanomaterials sciences owing to their unique structures and properties, which could be found neither in nanoparticles with several nanometer diameters nor in organometallic complexes. Along with the chemical nature of each element, properties of nanoclusters change dramatically with size parameters, making nanoclusters strong potential candidates for future tailor-made materials; these nanoclusters are expected to have attractive properties such as redox activity, catalysis, and magnetism. Alloying of nanoclusters additionally gives designer functionality by fine control of their electronic structures in addition to size parameters. Among binary nanoclusters, binary cage superatoms (BCSs) composed of transition metal (M) encapsulating silicon cages, M@Si, have unique cage structures of 16 silicon atoms, which have not been found in elemental silicon nanoclusters, organosilicon compounds, and silicon based clathrates. The unique composition of these BCSs originates from the simultaneous satisfaction of geometric and electronic shell-closings in terms of cage geometry and valence electron filling, where a total of 68 valence electrons occupy the superatomic orbitals of (1S)(1P)(1D)(1F)(2S)(1G)(2P)(2D) for M = group 4 elements in neutral ground state. The most important issue for M@Si BCSs is fine-tuning of their characters by replacement of the central metal atoms, M, based on one-by-one adjustment of valence electron counts in the same structure framework of Si cage; the replacement of M yields a series of M@Si BCSs, based on their superatomic characteristics. So far, despite these unique features probed in the gas-phase molecular beam and predicted by quantum chemical calculations, M@Si have not yet been isolated. In this Account, we have focused on recent advances in synthesis and characterizations of M@Si BCSs (M = Ti and Ta). A series of M@Si BCSs (M = groups 3 to 5) was found in gas-phase molecular beam experiments by photoelectron spectroscopy and mass spectrometry: formation of halogen-, rare-gas-, and alkali-like superatoms was identified through one-by-one tuning of number of total valence electrons. Toward future functional materials in the solid state, we have developed an intensive, size-selected nanocluster source based on high-power impulse magnetron sputtering coupled with a mass spectrometer and a soft-landing apparatus. With scanning probe microscopy and photoelectron spectroscopy, the structure of surface-immobilized BCSs has been elucidated; BCSs can be dispersed in an isolated form using C fullerene decoration of the substrate. The intensive nanocluster source also enables the synthesis of BCSs in the 100-mg scale by coupling with a direct liquid-embedded trapping method into organic dispersants, enabling their structure characterization as a highly symmetric "metal-encapsulating tetrahedral silicon-cage" (METS) structure with Frank-Kasper geometry.

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“…For example, the ground state structures of M@Si 16 (M = transition metal atom including RE metal atom) tend to be fullerene‐like configuration when radii of M are larger than 2.09 Å, but to be Frank‐Kasper (FK) motif when radii of M atom are less than or equal to 2.09 Å. That is, M@Si 16 for M = Y, La‐Lu, Zr, and Hf is fullerene‐like configuration, and that for M = Sc, Ti, and Ta is FK geometry …”

Section: Resultsmentioning

confidence: 99%

Structural stability and evolution of terbium‐doped silicon clusters and influence of 4f → 5d electronic transition mechanism on magnetism and appearance of photoelectron spectroscopy for TbSi_n^0/− (n = 6‐18) clusters

Yang

Cheng

2019

Int J of Quantum Chemistry

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The global minimal structures of terbium-doped Si clusters and their anions TbSi n 0/− (n = 6-18) are confirmed by employing the ABCluster unbiased global search technique combined with a B2PLYP double-hybrid density functional and comparing consistency of simulated and experimental photoelectron spectroscopy (PES). The results demonstrated that structural evolution patterns for neutral clusters prefer Tb-substitutional to Tb-encapsulated configuration starting from n = 16. While for the corresponding anionic clusters, the growth pattern adopts Tb-linked structures to encapsulated motif. The Natural Population Analysis revealed that the 4f electrons of Tb atom in TbSi n 0/− (n = 6-18) clusters participate in bonding. The way to participate in bonding is one 4f electron transition to 5d orbital ([Xe]6s 2 4f 9 ! [Xe]6s 2 4f 8 5d 1), which significantly affects the cluster's magnetism and appearance of PES. The total magnetic moments of neutral TbSi n and the corresponding anions maintain at 7 μB and 6 μB, respectively, which are larger than that of an isolated Tb atom. The HOMO-LUMO energy gap, relative stability, and chemical bonding analysis demonstrated that superatomic TbSi 16 − cluster is a magic cluster with fine thermodynamic and moderate chemical stability. K E Y W O R D S terbium-doped Si clusters, structural evolution patterns, cluster's magnetism 1 | INTRODUCTION Rare earth (RE) is known as the industrial "gold." RE-doped semiconductors such as silicon exhibits novel light electron magnetic and chemical properties and yields interesting features that are extremely useful in broad applications, from microelectronic industries to energy, materials, and chemical industries. For instance, erbium silicides are the excellent silicon-based photonic source: the light emitting diode, fiber amplifier, or device of the photomedicine. [1] NdFeB magnets are widely used in small size direct current motor, hard disks, mobile phones, battery-powered tools, and other electronic products. [2,3] RE silicides play a vital role in refining, desulfurization, neutralizing low-melting harmful impurities, and improving the properties of steels. [4] Terbium silicide is an ideal device, which has immeasurable potential in field emission cathode, hydrogen storage material, internal photoemission infrared detector, and so forth. It is also used in semiconductor industry as large-scale integrated circuits, Ohmic contacts, and rectifying contacts, owing to the interfaces of terbium and silicon have good lattice matching, sharp interfaces, low Schottky barrier heights, high conductivity, and excellent thermal stability. [5,6] Furthermore, terbium silicides can be formed by a self-assembly process, which is a powerful tool overcoming the miniaturization limit of traditional lithography-based fabrication methods of electronic devices like

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Charge Transfer Complexation of Ta-Encapsulating Ta@Si₁₆ Superatom with C₆₀

Cited by 34 publications

References 55 publications

Li₈Si₈, Li₁₀Si₉, and Li₁₂Si₁₀: Assemblies of Lithium‐Silicon Aromatic Units

Li₈Si₈, Li₁₀Si₉, and Li₁₂Si₁₀: Assemblies of Lithium‐Silicon Aromatic Units

Synthesis and Characterization of Metal-Encapsulating Si₁₆ Cage Superatoms

Structural stability and evolution of terbium‐doped silicon clusters and influence of 4f → 5d electronic transition mechanism on magnetism and appearance of photoelectron spectroscopy for TbSi_n^0/− (n = 6‐18) clusters

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Charge Transfer Complexation of Ta-Encapsulating Ta@Si16 Superatom with C60

Cited by 34 publications

References 55 publications

Li8Si8, Li10Si9, and Li12Si10: Assemblies of Lithium‐Silicon Aromatic Units

Li8Si8, Li10Si9, and Li12Si10: Assemblies of Lithium‐Silicon Aromatic Units

Synthesis and Characterization of Metal-Encapsulating Si16 Cage Superatoms

Structural stability and evolution of terbium‐doped silicon clusters and influence of 4f → 5d electronic transition mechanism on magnetism and appearance of photoelectron spectroscopy for TbSin0/− (n = 6‐18) clusters

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Charge Transfer Complexation of Ta-Encapsulating Ta@Si₁₆ Superatom with C₆₀

Li₈Si₈, Li₁₀Si₉, and Li₁₂Si₁₀: Assemblies of Lithium‐Silicon Aromatic Units

Li₈Si₈, Li₁₀Si₉, and Li₁₂Si₁₀: Assemblies of Lithium‐Silicon Aromatic Units

Synthesis and Characterization of Metal-Encapsulating Si₁₆ Cage Superatoms

Structural stability and evolution of terbium‐doped silicon clusters and influence of 4f → 5d electronic transition mechanism on magnetism and appearance of photoelectron spectroscopy for TbSi_n^0/− (n = 6‐18) clusters