Small copper-doped silicon clusters CuSin (n = 4–10) and their anions: structures, thermochemistry, and electron affinities

Lin, Lin; Yang, Jucai

doi:10.1007/s00894-015-2702-5

Cited by 10 publications

(5 citation statements)

References 77 publications

(159 reference statements)

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“…In an early study, Kumar et al 58 considered several isomers, including isomers (a), (c), and (f) in Figure 31. Other theoretical studies have explored a number of guest atoms, including Be, 67,467 V, 394 Ti, 394 Mn, 420 Fe, 375,376,380,383,389,405,434 Co, 375,399,405 Ni, 58,392,394,397,405,436 Cu, 397,406,414,436,445 Zn, 397 Pd, 58,392,394 Pt, 58,392,394 and Au. 394,436 We have considered cage isomers in Figure 31 for each dopant and also allowable spin states in our own PBE0 calculations to determine the most stable structure.…”

Section: Endohedrally Doped Silicon Cages By Size From Calculationsmentioning

confidence: 99%

“…We start the discussion of endohedral M@Si n cages from n = 10, since many calculations indicated that Si 10 is the smallest cage to completely enclose a guest atom. ,,,,,,,,,,, As shown in Figure , six possible structural isomers for the endohedral M@Si 10 cages have been considered: (a) a bicapped tetragonal antiprism, (b) fullerene type, (c) an isomer with triangular and (distorted) rhombi faces, (d and e) fullerene-like with all atoms having three neighbors on the cage but having a triangle in addition to pentagons and rhombi, and (f) an isomer having a hexagon instead of a pentagon. In an early study, Kumar et al considered several isomers, including isomers (a), (c), and (f) in Figure .…”

Section: Endohedrally Doped Silicon Cagesmentioning

confidence: 99%

“…In an early study, Kumar et al considered several isomers, including isomers (a), (c), and (f) in Figure . Other theoretical studies have explored a number of guest atoms, including Be, , V, Ti, Mn, Fe, ,,,,,, Co, ,, Ni, ,,,,, Cu, ,,,, Zn, Pd, ,, Pt, ,, and Au. , We have considered cage isomers in Figure for each dopant and also allowable spin states in our own PBE0 calculations to determine the most stable structure. Upon relaxation, Ti, Cr, Zn, or Au dopant atom escapes from the interior of the Si 10 cage, as it is too small to accommodate these guest atoms.…”

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 Cages By Size From Calculationsmentioning

confidence: 99%

Section: Endohedrally Doped Silicon Cagesmentioning

confidence: 99%

Section: Endohedrally Doped Silicon Cagesmentioning

confidence: 99%

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Endohedrally Doped Cage Clusters

2020

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“…Theoretically, to investigate the geometries of the different types of clusters, various methods have been used. We quote the basin hopping method into the Monte Carlo simulation [11-13, 30, 40-43] and DFT level of theory [22][23][24][25][26][27][28][29].…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic, Structure, and Thermodynamic Properties of the Lithium Cation Emerged in the Small Neon Clusters Li+-Nen (n=1-20).

Mabrouk

Dhiflaoui

Béjaoui

et al. 2023

Preprint

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The geometric structures and the relative stability of the Li+−Nen clusters, with n = 1–20, have been computed using pairwise model potential and density functional theory (DFT) method. The potential energy surface employed in these calculations is based on the Li+-Ne, Ne-Ne and many body interactions V3B. A series of methods and basis sets have been tested by reproduce correctly the experimental Li+-Ne and Ne-Ne potential energies. In addition, both Li+-Ne and Ne-Ne numerical potentials have been fitted by several analytical expressions as Tang and Toennies (TT), Extended Lennard Jones (ELJ) and Lennard-Jones (LJ) formula. The most stable structures of Li+-Nen clusters up to n = 20 have been optimized at Basin Hopping Monte Carlo (BHMC) method. The accuracy of our pairwise potential model has been confirmed by re-optimization at the DFT level of theory. The relative stabilities of Li+-Nen clusters are discussed by calculating the energy per neon atom, the first derivative, the fragmentation energy and the second derivative as well as the Highest Occupied Molecular orbital (HOMO)–Lowest Unoccupied Molecular Orbital(LUMO) energy gap with the size of the clusters. It was shown that n=6, 8, 12, 14, 16 and 17 correspond to the magic numbers. Finally, thermodynamic properties are calculated and showed that the formation process of Li+-Nen clusters is endothermic and non-spontaneous.

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“…The solvation of Li + with molecular solvents has been addressed by various methods, − ,− ,− while similar studies involving rare-gas atoms are scarce in the literature. However, Froudakis et al .…”

Section: Introductionmentioning

confidence: 99%

Pairwise Model Potential and DFT Study of Li⁺Ne_n Clusters (n = 1–20): The Structural, Electronic, and Thermodynamic Properties

Mabrouk,

Dhiflaoui,

Bejaoui

et al. 2023

ACS Omega

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The structural properties, relative stabilities, electronic, and thermodynamic properties, of Li + Ne n (n = 1−20) clusters have been studied based on a pairwise model and density functional theory (DFT) methods. In the pairwise method, the potential energy surface considered interactions between Li + Ne, Ne − Ne, and many-body term. For the DFT calculations, the B3LYP functional combined with the 6−311 + + G (2d,2p) basis sets has been employed. In both methods, the Li + Ne 6 cluster demonstrated high stability with an octahedral structure, where the Li + cation was surrounded by Ne atoms. Thus, the octahedral Li + Ne 6 structure was considered to be the core for larger cluster sizes. Relative stabilities were assessed based on binding energies, second-order differences of energies, transition dipole moment, and HOMO−LUMO energy gaps. Furthermore, thermodynamic properties were calculated, revealing that the formation process of Li + Ne n clusters is endothermic and nonspontaneous.

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Small copper-doped silicon clusters CuSin (n = 4–10) and their anions: structures, thermochemistry, and electron affinities

Cited by 10 publications

References 77 publications

Endohedrally Doped Cage Clusters

Endohedrally Doped Cage Clusters

Spectroscopic, Structure, and Thermodynamic Properties of the Lithium Cation Emerged in the Small Neon Clusters Li+-Nen (n=1-20).

Pairwise Model Potential and DFT Study of Li⁺Ne_n Clusters (n = 1–20): The Structural, Electronic, and Thermodynamic Properties

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Small copper-doped silicon clusters CuSin (n = 4–10) and their anions: structures, thermochemistry, and electron affinities

Cited by 10 publications

References 77 publications

Endohedrally Doped Cage Clusters

Endohedrally Doped Cage Clusters

Spectroscopic, Structure, and Thermodynamic Properties of the Lithium Cation Emerged in the Small Neon Clusters Li+-Nen (n=1-20).

Pairwise Model Potential and DFT Study of Li+Nen Clusters (n = 1–20): The Structural, Electronic, and Thermodynamic Properties

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Pairwise Model Potential and DFT Study of Li⁺Ne_n Clusters (n = 1–20): The Structural, Electronic, and Thermodynamic Properties