Structure, stability, absorption spectra and aromaticity of the singly and doubly silicon doped aluminum clusters AlnSim0/+ with n = 3–16 and m = 1, 2

Tam, Nguyen Minh; Duong, Long Van; Cuong, Ngo Tuan; Nguyen, Minh Tho

doi:10.1039/c9ra04004h

Cited by 8 publications

(7 citation statements)

References 66 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…These systems will be discussed in the subsequent sections. Recently, Tam et al 212 have studied the atomic and electronic structures of singly and doubly Si doped aluminum clusters in neutral and cationic states using B3LYP/6-311+G(d) and (U)CCSD(T)/ cc-pvTZ calculations. They also found Si@Al 12 and [Al 11 Si 2 ] + clusters to be magic.…”

Section: Endohedral Clusters Of Aldevelopment Of Metal Clusters As S...mentioning

confidence: 99%

Endohedrally Doped Cage Clusters

2020

View full text Add to dashboard Cite

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.

show abstract

Section: Endohedral Clusters Of Aldevelopment Of Metal Clusters As S...mentioning

confidence: 99%

Endohedrally Doped Cage Clusters

2020

View full text Add to dashboard Cite

show abstract

“…This algorithm has been used in previous studies and shown to be highly efficient for systems containing different components. 18,[44][45][46] Another way of generating the initial isomers is a manual substitution by a Sc-atom at all Al positions of the well-known icosahedron Al 13 to generate the Al 12 Sc structures, and successively for the following sizes with more Sc atoms. The search also includes the shapes of other 13-atom clusters that have previously been reported.…”

Section: Methodsmentioning

confidence: 99%

“…17 Moreover, a recent study on singly and doubly silicon doped aluminum clusters reported that both neutral and cationic states of Al 11 Si 2 keep on favoring the icosahedral shape with one Si dopant embedded at the central position, whereas the remaining Si atom substitutes an external Al position of the icosahedron Al 13 . 18 Similarly, another study of Al 12 X clusters at both neutral and cationic states, with dopant X being a pentavalent atom including P, As, Sb and Bi, also showed that the P atom prefers to be at the center of the Al 12 icosahedron whereas the rest of the dopants favor occupancy of a vertex site due to their larger size. 19 Previous studies on transition metal doped aluminum clusters also reported that an icosahedral structure can be composed by 12 aluminum atoms plus a transition metal dopant such as Co, Ni, Cu, and Zn.…”

Section: Introductionmentioning

confidence: 96%

The binary aluminum scandium clusters Al_xSc_y with x + y = 13: when is the icosahedron retained?

et al. 2021

Self Cite

View full text Add to dashboard Cite

show abstract

“…Initial geometries of the small binary boron and silicon clusters B 2 Si 3 q and B 3 Si 2 p with the charge q = −2, −1, 0, and 2 and p = −3, −2, −1, 0, and 1 are constructed independently by using a stochastic search algorithm which was implemented by our group − along with a manual search in view of the rather small number of atoms involved. All guess geometries are optimized using the density functional TPSSh in conjunction with the 6-311+G(d) basis set.…”

Section: Computational Methodsmentioning

confidence: 99%

Boron Silicon B₂Si₃^qand B₃Si₂^pClusters: The Smallest Aromatic Ribbons

et al. 2022

Self Cite

View full text Add to dashboard Cite

The small binary boron silicon clusters B2Si3 q with q going from −2 to +2 and B3Si2 p with p varying from −3 to +1 were reinvestigated using quantum chemical methods. The thermodynamic stability of these smallest ribbon structures is governed by both Hückel and ribbon models for aromaticity. The more negative the cluster charge, the more ribbon character is shown. In contrast, the more positive the charge state, the more pronounced the Hückel character becomes. The ribbon aromaticity character can also be classified into ribbon aromatic, semiaromatic, antiaromatic, and triplet aromatic when the electron configuration of a ribbon structure is described as [...π 2(n+1) σ 2n ], [...π 2n+1 σ 2n ], [...π 2n σ 2n ], and [...π 2n+1 σ 2n–1 ], respectively. Geometry optimizations of the B2Si3 lowest-energy structure by some density functional theory (DFT) functionals result in a nonplanar shape because it possesses an antiaromatic ribbon character. However, its π aromaticity assigned by the Hückel rule is stronger in such a way that several other DFT and coupled-cluster theory CCSD(T) calculations show that B2Si3 is indeed stable in a planar form (C s ). A new global equilibrium structure for the anion B2Si3 2–, which is a ribbon semiaromatic species, was identified. Some benchmark tests were also carried out to evaluate the performance of popular methods for the treatment of binary B–Si clusters. At odds with some previous studies, we found that with reference to the high accuracy CCSD(T)/CBS method, the hybrid TPSSh functional is reliable for a structure search, whereas the hybrid B3LYP functional is more suitable for simulations of some experimental spectroscopic results.

show abstract

Structure, stability, absorption spectra and aromaticity of the singly and doubly silicon doped aluminum clusters Al_nSi_m^0/+ with n = 3–16 and m = 1, 2

Abstract: The isoelectronic “magic” clusters with 40 shell electrons have enhanced thermochemical stability.

Cited by 8 publications

References 66 publications

Endohedrally Doped Cage Clusters

Endohedrally Doped Cage Clusters

The binary aluminum scandium clusters Al_xSc_y with x + y = 13: when is the icosahedron retained?

Boron Silicon B₂Si₃^qand B₃Si₂^pClusters: The Smallest Aromatic Ribbons

Contact Info

Product

Resources

About

Structure, stability, absorption spectra and aromaticity of the singly and doubly silicon doped aluminum clusters AlnSim0/+ with n = 3–16 and m = 1, 2

Abstract: The isoelectronic “magic” clusters with 40 shell electrons have enhanced thermochemical stability.

Cited by 8 publications

References 66 publications

Endohedrally Doped Cage Clusters

Endohedrally Doped Cage Clusters

The binary aluminum scandium clusters AlxScy with x + y = 13: when is the icosahedron retained?

Boron Silicon B2Si3qand B3Si2pClusters: The Smallest Aromatic Ribbons

Contact Info

Product

Resources

About

Structure, stability, absorption spectra and aromaticity of the singly and doubly silicon doped aluminum clusters Al_nSi_m^0/+ with n = 3–16 and m = 1, 2

The binary aluminum scandium clusters Al_xSc_y with x + y = 13: when is the icosahedron retained?

Boron Silicon B₂Si₃^qand B₃Si₂^pClusters: The Smallest Aromatic Ribbons