Computational investigation on the endohedral borofullerenes M@B40 (M = Sc, Y, La)

Jin, Peng; Hou, Qinghua; Tang, Chengchun; Chen, Zhongfang

doi:10.1007/s00214-014-1612-4

Cited by 75 publications

(58 citation statements)

References 81 publications

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“…Unlike C 60 , boron forms cluster bonds by both s and p orbitals, which requires the use of 40 and its ions computed at the GIAO-PBE/6-311+G* and GIAO-PBE0/6-311+G* levels of theory based on the PBE0/6-31G* structures tensor surface harmonics [38,39]. Analogous to C 60 , B 40 is widely used in metalloborospherenes [2,40] or as hydrogen storage materials [41]. Furthermore, as superatom, because B 40 is highly robust and dynamically stable at high temperatures [1], so it may bring outburst of density of states and has potential applications in high-temperature superconductivity [42].…”

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confidence: 99%

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All-boron fullerene B40: a superatomic structure

Wang

2017

Sci. China Mater.

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By means of the first-principles calculations, we reveal that B 40 presents superatomic properties. It not only has superatomic 1S, 1P, 1D and 1F orbitals, but also has superatomic orbitals 2S, 2P, 2D and 2F. The superatomic 2F orbital of B 40 is partially occupied, thus adding six electrons to the cluster leads to a superatomic structure of fully occupied shells. , were also optimized at PBE0/ 6-31G* level. Frequency analyses were performed at the same level of theory to characterize the nature of the stationary points. Both B 40 and B 40 6− are true local minima, but B 40 8+ with fully occupied shell is a high order saddle point. Following the imaginary modes of B 40 8+ leads to the true local minimum without full-filled shell. The optimized geometries from different functionals are rather similar, and we only discuss the computational results from PBE0 because it has been tested extensively in previous works and found to be suitable for boron clusters [1,[20][21][22]. To investigate the electron delocalization or aromaticity of B 40 and its charged species, we calculated NICS (in ppm) [23,24] at the cage centers of the optimized geometries of the empty cage molecules using the gauge-independent atomic orbital (GIAO) method [25]. The verification of B 40 using PBE0/6-311 +G* level is shown in Table S2 in SI. All computations are carried out using the Gaussian09 package [26].Our calculations show that the ground state of B 40 fullerene (D 2d ) is non-spin-polarized singlet, with the low and high energy molecular orbitals (MOs) displayed in Figs 1, 2, respectively. Among the low-energy MOs, a double-occupied MO 7a 1 (marked by black) resembles an s-like atomic orbital, thus we call it the 1S superatomic orbital (that is, molecular orbital) for B 40 , and the specific orbital composition analyses are described in the fol-

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confidence: 99%

“…Subsequently, the stabilities and electronic properties of endohedral metal complexes of B 40 have also been investigated [2][3][4]. Among the clusters with various sizes, those deemed "superatoms" exhibit enhanced stabilities due to the electronic shell closing [5].…”

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All-boron fullerene B40: a superatomic structure

Wang

2017

Sci. China Mater.

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“…Soon after, the cage cluster B 39 − was also produced via laser vaporization30. The first observation of the borospherene has aroused interest in all-boron fullerenes and their derivatives such as dynamical behavior of B 40 31, hydrogen storage capacity of Ti-decorated B 40 32, experimental and theoretical studies of B 28 − and B 29 − borospherenes3334, structures and electronic properties of metalloborospherenes (Ca@B 40 , Be&B 40 , Sc@B 40 , Li&B 40 , Na@B 40 , Ca@B 39 + , Ca@B 38 , Ca@B 37 − and Li 4 &B 36 )35363738394041, and spectral properties of borospherenes4243.…”

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Structures, stabilities and spectral properties of borospherene B44− and metalloborospherenes MB440/− (M = Li, Na, and K)

Zhang

Long

et al. 2017

Sci Rep

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Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations are carried out to study the stabilities, photoelectron, infrared, Raman and electronic absorption spectra of borospherene B44− and metalloborospherenes MB440/− (M = Li, Na, and K). It is found that all atoms can form stable exohedral metalloborospherenes M&B440/−, whereas only Na and K atoms can be stably encapsulated inside B440/− cage. In addition, relative energies of these metalloborospherenes suggest that Na and K atoms favor exohedral configuration. Importantly, doping of metal atom can modify the stabilities of B44 with different structures, which provides a possible route to produce stable boron clusters or metalloborospherenes. The calculated results suggest that B44 tends to get electrons from the doped metal. Metalloborospherenes MB44− are characterized as charge-transfer complexes (M2+B442−), where B44 tends to get two electrons from the extra electron and the doped metal, resulting in similar features with anionic B442−. In addition, doping of metal atom can change the spectral features, such as blueshift or redshift and weakening or strengthening of characteristic peaks, since the extra metal atom can modify the electronic structure. The calculated spectra are readily compared with future spectroscopy measurements and can be used as fingerprints to identify B44− and metalloborospherenes.

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“…[35,36] Larger metal-doped boron clusters have been considered computationally,i ncluding the Fe-centered B 14 and B 16 double rings, and metal-centered B 18 ,B 20 ,and B 24 cages. [37,38] Even though the proposed fullerene-like B 80 was shown to be ah igh energy isomer, [39] the recent discovery of borospherenes [6,40] suggested the possibility of endohedral borospherenes, [41][42][43] like the family of endohedral fullerenes. [44] Thev iability of endohedral borospherenes requires the systematic characterization of doped boron clusters.Recently, the observation and characterization of the largest dopedboron clusters,CoB 16 À ,was reported, revealing aremarkable drum-like structure with the Co atom coordinated by two connected B 8 rings.…”

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The Planar CoB₁₈⁻ Cluster as a Motif for Metallo‐Borophenes

Jian

Chen

et al. 2016

Angewandte Chemie

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Monolayer‐boron (borophene) has been predicted with various atomic arrangements consisting of a triangular boron lattice with hexagonal vacancies. Its viability was confirmed by the observation of a planar hexagonal B36 cluster with a central six‐membered ring. Here we report a planar boron cluster doped with a transition‐metal atom in the boron network (CoB18−), suggesting the prospect of forming stable hetero‐borophenes. The CoB18− cluster was characterized by photoelectron spectroscopy and quantum chemistry calculations, showing that its most stable structure is planar with the Co atom as an integral part of a triangular boron lattice. Chemical bonding analyses show that the planar CoB18− is aromatic with ten π‐electrons and the Co atom has strong covalent interactions with the surrounding boron atoms. The current result suggests that transition metals can be doped into the planes of borophenes to create metallo‐borophenes, opening vast opportunities to design hetero‐borophenes with tunable chemical, magnetic, and optical properties.

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Computational investigation on the endohedral borofullerenes M@B40 (M = Sc, Y, La)

Cited by 75 publications

References 81 publications

All-boron fullerene B40: a superatomic structure

All-boron fullerene B40: a superatomic structure

Structures, stabilities and spectral properties of borospherene B44− and metalloborospherenes MB440/− (M = Li, Na, and K)

The Planar CoB₁₈⁻ Cluster as a Motif for Metallo‐Borophenes

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Computational investigation on the endohedral borofullerenes M@B40 (M = Sc, Y, La)

Cited by 75 publications

References 81 publications

All-boron fullerene B40: a superatomic structure

All-boron fullerene B40: a superatomic structure

Structures, stabilities and spectral properties of borospherene B44− and metalloborospherenes MB440/− (M = Li, Na, and K)

The Planar CoB18− Cluster as a Motif for Metallo‐Borophenes

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The Planar CoB₁₈⁻ Cluster as a Motif for Metallo‐Borophenes