Probing the geometric structures and bonding properties in Nb2Si20−/0 clusters by density functional theory calculations

Lu, Sheng-Jie; Wu, Li-Shun; Lin, Feng

doi:10.1016/j.cplett.2018.08.041

Cited by 15 publications

(5 citation statements)

References 41 publications

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“…In addition to the singly metal doped Si n cages, stable endohedral Si n cages ( n ≤ 20) doped with multiple metal atoms (up to three) have also been considered. For smaller cages with no more than 14 vertices, one metal dopant occupies the cage center, while the other one or two metal atoms stay on the surface sites and participate in the cage framework to form a silicon–metal polyhedron. ,,,, On the contrary, large Si n clusters with n ≥ 16 are able to accommodate two metal (M) atoms in the cage, ,,,,,,− forming a variety of M 2 @Si n endohedral complexes usually with ellipsoid or fused-cage shape. Beyond the Si 20 host cage, Gao and Zeng proposed that a tetrahedral fullerene cage Si 28 , which is indeed the silicon counterpart of T d -C 28 fullerene, can be fully stabilized by encapsulating a tetrahedral 4-atom metal cluster, i.e., Al 4 or Ga 4 .…”

Section: Endohedrally Doped Silicon Cagesmentioning

confidence: 99%

“…On the theoretical side, the lowest-energy geometries and energetic stabilities of dual transition metal doped Si 20 clusters (i.e., M 2 @Si 20 ) have been explored by several groups. Depending on the size and number of d electrons of the metal atom, as well as the M–M bond strength, there are three types of Si 20 framework structures for endohedral doping, i.e., elongated dodecahedron cage (Figure a) for W 2 , Zr 2 , V 2 , and Nb 2 , , double hexagonal prisms stacked structure (Figure b) for Ti 2 , and FK structure as the combination of two M@Si 10 endohedral structural units (Figure c) for Fe 2 . In an early DFT study, a rich class of M 2 @Si 20 clusters possessing perfect, stacked, or deformed double hexagonal prisms have been predicted for M = V, Cr, Mo, Hf, Fe, Co, Re, and Os.…”

Section: Endohedrally Doped Silicon Cagesmentioning

confidence: 99%

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Endohedrally Doped Cage Clusters

2020

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The discovery of carbon fullerene cages and their solids opened a new avenue to build materials from stable cage clusters as “artificial atoms” or “superatoms” instead of atoms. However, cage clusters of other elements are generally not stable. In 2001, ab initio calculations showed that endohedral doping of Zr and Ti atoms leads to highly stable Zr@Si16 fullerene and Ti@Si16 Frank–Kasper polyhedral clusters with large HOMO–LUMO gaps. In 2002, Zr@Ge16 was shown to form a Frank–Kasper polyhedron, suggesting the possibility of designing novel clusters by tuning endohedral and cage atoms. These results were subsequently confirmed from experiments. In the past nearly two decades, many experimental and theoretical studies have been carried out on different clusters, and many very stable cage clusters with possibly high abundance have been found by endohedral doping. Indeed in 2017, Ta@Si16 and Ti@Si16 cage clusters have been synthesized in bulk quantity of about 100 mg using a dry-chemistry method, giving rise to a new hope of developing cluster-based materials in macroscopic quantity besides the well-known C60 fullerene solid. Also, wet-chemistry methods have been used to synthesize endohedrally doped clusters as well as ligated clusters and their solids, which auger well for the development of novel nanostructured materials using atomically precise clusters with unique properties. In this comprehensive review, we present results of many such developments in this fast-growing field including (i) endohedrally doped Al, Ga, and In clusters, (ii) small endohedral carbon fullerene cages with ≤ 28 carbon atoms, (iii) metal doped boron cages, (iv) endohedrally doped cages of group 14 elements (Si, Ge, Sn, and Pb), (v) coinage metal (Cu, Ag, Au) cages doped with a transition metal atom as well as their ligated clusters and crystals, (vi) endohedrally doped cages of compound semiconductors, and (vii) multilayer Matryoshka cages and core–shell structures. In a large number of cases, we have performed ab initio calculations to present updated results of the most stable atomic structures and fundamental electronic properties of the endohedrally doped cage clusters. We discuss electronic, magnetic, optical, and catalytic properties in order to shed light on their potential applications. The stability of the doped cage clusters has been correlated to the concept of filling the electronic shells for superatoms such as within a spherical potential model and also using various electron counting rules including Wade–Mingos rules, systems with 18 and 32 electrons, and the spherical aromaticity rule. We also discuss cluster–cluster interaction in cluster dimers and assemblies of some of the promising doped cage clusters in different dimensions. Finally, we give a perspective of this field with a bright future.

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Section: Endohedrally Doped Silicon Cagesmentioning

confidence: 99%

Section: Endohedrally Doped Silicon Cagesmentioning

confidence: 99%

Endohedrally Doped Cage Clusters

2020

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“…The structures and properties of a large number of niobiumdoped silicon clusters have been investigated using both experimental and theoretical methods. [5][6][7][8][9][10][11][12][13][14][15][16][17] Regarding the NbSi 4 −/0 clusters, the anionic clusters were synthesized and analyzed using photoelectron spectroscopy with 266 nm wavelength photons. 17 The photoelectron spectrum of © 2024 Vietnam Academy of Science and Technology and Wiley-VCH GmbH.…”

Section: Introductionmentioning

confidence: 99%

“…Investigating Nb‐doped silicon clusters contributes to a deeper understanding of the microscopic mechanisms in NbSi films and metal‐semiconductor alloys, while providing valuable information for cluster‐assembled material production. The structures and properties of a large number of niobium‐doped silicon clusters have been investigated using both experimental and theoretical methods 5–17 . Regarding the NbSi 4 −/0 clusters, the anionic clusters were synthesized and analyzed using photoelectron spectroscopy with 266 nm wavelength photons 17 .…”

Section: Introductionmentioning

confidence: 99%

Unveiling geometric and electronic structures of NbSi₄^−/0 clusters and electron detachments of the anionic cluster: A quantum chemical investigation

Tran

2024

Vietnam Journal of Chemistry

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This article presents computational insights into the geometric and electronic structures of NbSi4−/0 clusters using density functional theory and the CASSCF/CASPT2 method. The anionic and neutral ground states are identified as the 1A′ and 2A′ states, respectively, within a trigonal bipyramidal isomer where the Nb atom occupies the equatorial position. The adiabatic detachment energy for the transition from the anionic ground state 1A′ to the neutral ground state 2A′ is estimated to be 2.30 eV. Additionally, an evaluation of the vertical detachment energies for transitions to the neutral states 12A′, 12A″, 22A′, 22A″, 32A′, 32A″, and 42A′ yields respective values of 2.42, 2.78, 2.94, 3.34, 3.86, 4.08, and 4.28 eV. These computed electron detachment energies successfully account for all five bands observed in the photoelectron spectrum of the anionic cluster. Furthermore, the Franck–Condon factor simulations reveal extensive vibrational progressions associated with the transition to the neutral ground state 12A′, manifesting as an unresolved broad band at 2.41 eV in the spectrum.

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“…Transition-metal-doped silicon clusters have been studied to identify stable structures that can serve as building blocks for nanomaterials. It has been discovered that a large number of transition-metal-doped silicon clusters have stable cage structures. − Both theoretical and experimental methods have been used to study the structures of silicon clusters doped with niobium. ,,− The structure of the neutral diatomic NbSi cluster was investigated with electron spin resonance spectroscopy . Based on a logical extrapolation of the experimental and theoretical information on ScO, TiN, VC, YO, ZrN, and NbC, the ground states of NbSi were assumed to be 2 Δ.…”

Section: Introductionmentioning

confidence: 99%

Electron Detachments of NbSi_n^–/0 (n = 1–3) Clusters from Density Matrix Renormalization Group-CASPT2 Calculations

Tran

2023

J. Phys. Chem. A

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The electronic states of NbSi n –/0/+ (n = 1–3) clusters have been explored using the state-of-the-art DMRG-CASPT2 method with relatively large active spaces. The leading configurations, bond distances, vibrational frequencies, and relative energies of the low-lying states were identified. Electron detachment energies of the anionic cluster and ionization energies of the neutral clusters were reported at the DMRG-CASPT2 level. The ground states of the NbSi n –/0/+ (n = 1–3) clusters were predicted as the 3Δ, 4Π, and 5Π states of the linear NbSi–/0/+, the 3A2, 4B1, and 3B1 states of cyclic NbSi2 –/0/+, and the 1A′, 2A′, and 3A″ states of tetrahedral NbSi3 –/0/+ isomers. The first feature in the photoelectron spectrum of NbSi– was attributed to the transitions from the anionic 3Δ ground state to the neutral 4Π, 4Δ, and 4Φ states, whereas the second feature was assigned to the transitions to the neutral 2Δ, 2Σ+, and 2Φ states. The first band in the photoelectron spectrum of NbSi3 – was ascribed to the transition from the anionic 1A′ ground state to the neutral 12A′ and 12A″ states; the second band was attributed to the transitions to 22A′, 22A″, and 32A′ states; and the third band was assigned to the transition to 32A′ states.

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Probing the geometric structures and bonding properties in Nb2Si20−/0 clusters by density functional theory calculations

Cited by 15 publications

References 41 publications

Endohedrally Doped Cage Clusters

Endohedrally Doped Cage Clusters

Unveiling geometric and electronic structures of NbSi₄^−/0 clusters and electron detachments of the anionic cluster: A quantum chemical investigation

Electron Detachments of NbSi_n^–/0 (n = 1–3) Clusters from Density Matrix Renormalization Group-CASPT2 Calculations

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Probing the geometric structures and bonding properties in Nb2Si20−/0 clusters by density functional theory calculations

Cited by 15 publications

References 41 publications

Endohedrally Doped Cage Clusters

Endohedrally Doped Cage Clusters

Unveiling geometric and electronic structures of NbSi4−/0 clusters and electron detachments of the anionic cluster: A quantum chemical investigation

Electron Detachments of NbSin–/0 (n = 1–3) Clusters from Density Matrix Renormalization Group-CASPT2 Calculations

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Unveiling geometric and electronic structures of NbSi₄^−/0 clusters and electron detachments of the anionic cluster: A quantum chemical investigation

Electron Detachments of NbSi_n^–/0 (n = 1–3) Clusters from Density Matrix Renormalization Group-CASPT2 Calculations