DFT study of [Fe@B36N36]n+ (n=2, 3) endohedral nanocages: Chemical reactivity, NBO analysis and thermochemistry

Oliaey, Ahmad Reza; Boshra, Asadollah

doi:10.1016/j.physe.2013.03.011

Cited by 11 publications

(7 citation statements)

References 34 publications

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“…Inspired by the experimental success, endohedral doping of a single atom or very small clusters (up to tetramers) in different B n N n ( n = 12, 16, 20, 24, 28, 36, 48) cages has been explored by numerous ab initio calculations. − The geometries of these BN cages are depicted in Figure . Intuitively, the smallest possible BN cage to contain a dopant atom is B 12 N 12 consisting of 6 tetragonal and 8 hexagonal BN rings with T h symmetry (Figure a).…”

Section: Endohedrally Doped Cages Of Compoundsmentioning

confidence: 99%

“…Experiments by Oku et al showed − that B 36 N 36 is the most frequently observed cage incorporating a guest metal atom. Therefore, encapsulation of various dopant atoms in the B 36 N 36 cage has been extensively studied by many groups. − Soon after the experimental observation of La@B 36 N 36 , Q. Wang et al performed spin-polarized calculations using a planewave basis and PW91 functional. They found that the endohedral La atom stays at an off-center position (1.18 Å from the cage center) and interacts weakly with the BN cage having an exothermic embedding energy of 0.89 eV.…”

Section: Endohedrally Doped Cages Of Compoundsmentioning

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 Cages Of Compoundsmentioning

confidence: 99%

Section: Endohedrally Doped Cages Of Compoundsmentioning

confidence: 99%

Endohedrally Doped Cage Clusters

2020

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“…Oku and co-workers reported a series of M@(BN) 36 [5][6][7] compounds and found the (BN) 36 energy gap decreased after introducing doping atoms inside the (BN) 36 cage. Several theoretical calculations were performed based on these experiments for metal clusters doped within BN cages [10][11][12][13][14][15][16][17][18][19]. Nigam et al used the plane wave base pseudo potential method [12,13] to prepare structural and magnetic isomers of transition metal (TM) clusters and showed they retained their magnetic character except for Cu 4 .…”

Section: Introductionmentioning

confidence: 99%

Electronic structure, stability and magnetic properties of small M1–4(M = Fe, Co, Ni) clusters encapsulated inside a (BN)48 cage

Liang

Jia

et al. 2015

Chemical Physics Letters

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“…To overcome this bottleneck, magnetic clusters should be placed inside a stable, insulating, and protective shield. Recently, small TM clusters inside (BN) cages have been synthesized, and their stabilities and magnetic properties have been investigated [8][9][10][11][12][13][14][15][16][17]. Oku and co-workers reported a series of M@(BN) 36 [8][9][10]; the energy gap of (BN) 36 was reduced by doping atoms inside the (BN) 36 cage.…”

Section: Introductionmentioning

confidence: 99%