Effects of endohedral element in B24N24 clusters on hydrogenation studied by molecular orbital calculations

Possibility of hydrogen gas storage in boron nitride (BN) clusters was investigated by molecular orbital calculations. Chemisorption calculation was carried out for B₂₄N₂₄ with changing endohedral elements in BN cluster to compare the bonding energy at nitrogen and boron, which showed that Li is a suitable element for hydrogenation to B₂₄N₂₄.     

Formation and structures of B36N36 and Y@B36N36 clusters studied by high-resolution electron microscopy and mass spectrometry

High-resolution electron microscopy, mass spectrometry and molecular mechanics/orbital calculations of the boron nitride-based clusters showed the formation of B₃₆N₃₆ and Y@B₃₆N₃₆. Image simulations of these clusters confirmed the proposed structure model.     

Characterizations of B and N heteroatoms as substitutional doping on structure,stability, and aromaticity of novel heterofullerenes evolved from the smallest fullerene cage C20: a density functional theory perspective

The structural stabilities and electronic properties of C₂₀ fullerene and some its incorporated boron and nitrogen derivatives are probed at B3LYP/AUG‐cc‐pVTZ level of theory. According to density functional theory results, the topology of inserted B or N heteroatoms in [20]‐fullerene perturbs strongly the stability, energy, geometry, charge, polarity, nucleus‐independent chemical shifts, aromaticity, and highest‐occupied molecular orbital and lowest‐unoccupied molecular orbital (HOMO–LUMO) gap of the resulting heterofullerenes. Vibrational frequency (υ_min) calculations show that except N₁₀C₁₀, all other B_bN_nC_{20‐(b + n)} heterofullerenes with b, and n = 0, 4, 5, 8, and 10 are true minima. The calculated band gaps (?E_HOMO–LUMO) of B₈C₁₂, and N₈C₁₂ (2.86 eV), show them the most stable heterofullerenes against electronic excitations. While 10 B substituting in equatorial position increase the conductivity of B₁₀C₁₀ through decreasing its band gaps, 10 N doping in equatorial position enhance stability of N₁₀C₁₀ against electronic excitations via increasing its band gaps. High natural bond orbital and Mulliken charge transfer on the surfaces of B atoms, especially B₅N₅C₁₀with five B–N bonds in the equatorial position, provokes further investigation on its possible application for hydrogen storage. Nucleus‐independent chemical shift values show that B₅N₅C₁₀ is the most aromatic species. The calculated heat of atomization per carbon (ΔH_at/C) of B₈C₁₂ shows it the most thermodynamic stable heterofullerenes of each. Copyright © 2016 John Wiley & Sons, Ltd.     

Formation and atomic structures of boron nitride nanohorns encaging boron nitride cluster

Boron nitride (BN) nanohorns were synthesized by arc-melting YB₆ powders. Method, and atomic structure models for BN nanohorns encaging Y@B₃₆N₃₆ were proposed from high-resolution electron microscopy. The molecular mechanics calculation indicated that BN clusters with metal atoms would be stabilized by being encaged in double-walled BN nanohorns.     

Formation of small single-layer and nested BN cages under electron irradiation of nanotubes and bulk material

12 N₁₂, B₁₆N₁₆ and B₂₈N₂₈ octahedra which were predicted to be magic clusters for the BN system from electronic structure calculations. Received: 2 March 1998     

Electronic structure of crystal-forming fulborenes B<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>N<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>

A general approach is formulated to the design of crystal-forming fullerene-like clusters X _n Y _n from which zeolite-like covalent crystals based on IV-IV, III-V, and II-VI binary semiconductor compounds with diamond-like sp ³ bonds can be constructed and synthesized by means of copolymerization through faces. A number of the smallest sized crystal-forming boron nitride clusters are constructed, such as the B₁₂N₁₂, B₁₆N1₆, B₁₈N₁₈, B₂₄N₂₄, B₃₆N₃₆, and B ₆₀N₆₀ fulborenes. The optimized configurations, electronic structures, charge transfers, band gaps, total energies, cohesive energies, and electron density maps of the clusters are calculated using the spin-restricted Hartree-Fock method in the 6–31G basis set. Comparative calculations of the B₆₀N₆₀ fulborene with the use of the density functional theory method have demonstrated that the spin-restricted Hartree-Fock method in the 6–31G basis set is optimum from the standpoint of the accuracy and efficiency.     

Effect of doping by boron,carbon, and nitrogen atoms on the magnetic and photocatalytic properties of anatase

The effect of doping of titanium dioxide with the anatase structure by boron, carbon, and nitrogen atoms on the magnetic and optical properties and the electronic spectrum of this compound has been investigated using the ab initio tight-binding linear muffin-tin orbital (TB-LMTO) band-structure method in the local spin density approximation explicitly including Coulomb correlations (LSDA + U) in combination with the semiempirical extended Hückel theory (EHT) method. The LSDA + U calculations of the electronic structure, the imaginary part of the dielectric function, the total magnetic moments, and the magnetic moments at the impurity atoms have been carried out. The diagrams of the molecular orbitals of the clusters Ti₃ X (X = B, C, N) have been calculated and the pseudo-space images of the molecular orbitals of the clusters have been constructed. The effect of doping on the nature and origin of photocatalytic activity in the visible spectral range and the specific features of the generation of ferromagnetic interactions in doped anatase have been discussed based on the analysis of the obtained data. It has been shown that, in the sequence TiO_{2 ? y} N _y → TiO_{2 ? y} C _y → TiO_{2 ? y} B _y (y = 1/16), the photocatalytic activity can increase with the generation of electronic excitations with the participation of impurity bands. The calculated magnetic moments for boron and nitrogen atoms are equal to 1 μ_B, whereas the impurity carbon atoms are nonmagnetic.     

Theoretical study on structure of boron nitride fullerenes

We propose the parameters of the Stillinger-Weber potential for hexagonal boron nitride (BN) structures. For the reliability of these parameters, the structural property of BN fullerenes is investigated. The stability of BN fullerenes increases with increasing the number of atoms, due to the reduction of the curvature effect of BN fullerenes. The structures of the relative stable fullerenes are B₁₆N₁₆, B₁₈N₁₈, B₂₂N₂₂, B₂₅N₂₅, and B₂₈N₂₈.     

Ab initio investigation of hydrogenation of (BN)12

Ab initio molecular orbital theory was used to examine the hydrogenation of a B₁₂N₁₂ molecule. The 1,2 addition of the 4,6 bond is an energetically favorable adsorption site in one-hydrogen-molecule adsorption. We found that the averaged bind energy of hydrogen molecule is maximized in B₁₂N₁₂H₁₂. The largest energy gaps of B₁₂N₁₂H₁₂ and B₁₂N₁₂H₂₄ suggest they have special stability. Moreover, calculation of the Gibbs free energy of the B₁₂N₁₂ + 12H₂ → B₁₂N₁₂H₂₄ reaction showed that this reaction becomes endothermic above 320 K.     

Hydrogen incorporation into BN fullerene-like nanostructures: A first-principles study

We performed density functional theory calculations to investigate the possibility of formation of endohedrally H@(BN)_n–fullerene (n: 24, 36, 60) and H@C₆₀ complexes for potential applications in solid-state quantum-computers. Spin-polarized approach within the generalized gradient approximation with the Perdew–Burke–Ernzerhof functional was used for the total energies and structural relaxation calculations. The calculated binding energies show that H atom being incorporated into B₆₀N₆₀ nanocage can form most stable complexes while the B₂₄N₂₄ and C₆₀ nanocages might form unstable complex with positive binding energy. We have also examined the penetration of an H atom into the respective nanocages and the calculated barrier energies indicate that the H atom prefers to penetrate into the B₂₄N₂₄ and B₆₀N₆₀ nanocages with barrier energy of about 0.47 eV (10.84 kcal/mol). Furthermore the binding characteristic is rationalized by analyzing the electronic structures. Our findings reveal that the B₆₀N₆₀ nanocage has fascinating potential application in future solid-state quantum-computers.     

Hydrogen storage capabilities of the most stable isomers of NanBm (m+n=6) clusters

The most stable isomers of NanBm(m+n=6) clusters and their hydrogen storage properties are investigated by means of density functional theory with a 6-311+G(d) basis set. To study the hydrogen storage properties,all of the stable structures of Na n BmHx (m+n=6) clusters have been optimized. It shows that boron atoms of Na n B m are separated from the other boron atoms,and form satellite BHx (x=3,4) clusters around the centre,which attach to the system by a bridging bond of a hydrogen atom or an Na atom. Compared with the hydrogen storage capabilities,the Na3B3 has the highest hydrogen storage capacity among Na n B m clusters. The binding energies,interaction energies of hydrogen atom with Na n B m clusters and second difference in energy of Na3B3Hx clusters have been calculated. The results show that the stability of the Na n B m H x clusters present an odd-even oscillatory effect,as the number of H atoms increases.     

Elemental and chemical-state mapping of boron carbide fracture surfaces

Samples of commercial B₄C and of reactive hot-pressed B₉C were fractured in situ in a scanning Auger microscopy (SAM) system. The B₄C fracture surfaces showed small areas of pore structures, as well as larger relatively smooth areas. Impurities (Cu, Si, S, Ca, N, O and Cr) were found in trace amounts in the pore areas. SAM maps were made of most of these impurities. The nitrogen was found by Auger lineshape in point Auger electron spectroscopy scans to be in the compound BN. Carbon was found on the surface in both boron carbide and as graphite. SAM was used to seperately map B in B₄C and B in BN, as well as C in B₄C and C in graphite, in a pore region. In the smooth areas of B₄C fracture surfaces fewer impurities were found. The carbon occured in B₄C and in localized carbon-rich areas which had graphite surface layers. In contrast, only B and C were found on the B₉C fracture surfaces; but the distributions of these elements were not homogenous. Carbon was found both in elemental form as graphite and chemically bound to boron as a carbide. In comparison with the graphite regions on the B₄C surfaces, the graphite areas on the B₉C fracture surfaces were not localized. The total surface area was nearly balanced between graphite and carbide regions. Argon ion bombardment revealed the graphite areas to be less than 100 nm thick.     

The nature of a selective peak in the BK-absorption edge spectrum and the electronic energy band structure of the crystal 3C BN0.99

A new interpretation of the nature of the resonance in the quantum-yield K spectra of boron in the crystal 3C BN is proposed. This interpretation is based on calculation of the electronic energy band structure of the nonstoichiometric boron nitride 3C BN_0.99, which is carried out by the local coherent potential method in the multiple-scattering approximation. The tops of the valence band and of the XANES range of nonstoichiometric and perfect crystals of boron nitride are compared with the x-ray photoelectron spectrum of 3C BN and the BK-absorption edge spectrum. The electronic states near the BK-absorption edge are modeled and discussed for the relaxed and metastable states caused by the formation of vacancies in the nitrogen sublattice.     

First-principles calculations of the structural, electronic and magnetic properties of BnN20−n (n = 6−18) clusters

The structures of B _n N_20 ? n    (n = 6?18), the clusters of boron nitride, are investigated by the density functional theory calculations. The structures of the obtained low-lying isomers can be described by the following six prototypes: single ring, double ring, three-ring, graphitic-like sheet, fullerene and others. B₁₀N₁₀ is demonstrated to be the most stable cluster against the nonstoichiometric ones. Nonzero magnetic moments, 1.999, 1.998, 2.000, 3.999 and 1.999μ _B respectively, are found in five B _n N_20?n (n = 6, 7, 11, 12, 13) clusters. Further analysis indicates that the magnetic moment of the B₆N₁₄ cluster is mainly originated from the N atoms, while those of others are from the B atoms. The magnetic moment are finally attributed to the interesting issues of the 2p electrons due to the breaking of local symmetries, the change of coordination number, charge distribution and orbital hybridization.     

Crystalline structures as an approximant of quasicrystal and distortion of B12 icosahedron in boron-rich solids: Search for semiconducting quasicrystal

Analyzing the crystalline structure of α- and β-rhombohedral boron as an approximant structure of a quasicrystal, atomic structures of two unit cells (prolate and oblate rhombohedra) of icosahedral quasicrystal are constructed. According to molecular orbital calculation, a neutral B ₁₂ H ₁₂ icosahedral cluster is distorted to a cubic or rhombohedral type by the Jahn–Teller effect. The distortion of B ₁₂ in the β-rhombohedral boron and K₂B₁₂H₁₂ has the same sign as the lowest energy distortion in the calculation. Among the α-rhombohedral type structures, the distortion of B₁₂ is correlated with the rhombohedral axis angle, and the angle is the closest to the icosahedral angle for B₆O and the distortion is the smallest for B–C. A meta-stable phase has been found on the way towards crystallization of amorphous B–C films.     

Geometric and electronic structures of B12C6N6 fullerene

An electron deficient fullerene B₁₂C₆N₆ is studied by using ab initio calculations. The structure is generated by replacing N with C in the B₁₂N₁₂ cage to ensure only B–C and B–N bonds are formed. All the possible isomers are optimized and the low energy structures are determined. C and N atoms in the low energy isomers are inclined to segregate and form B₂C₂ and B₂N₂ squares. Natural bond analysis shows that the atomic orbitals of B, C and N in this cage hybrid approximately in sp^2.3 and then form B–C and B–N bonds. The 2p orbitals perpendicular to the cage surface are partially occupied and the molecular orbitals formed by these orbitals are highly delocalized. The natural charge on N is about −1.17 in both B₁₂N₁₂ and B₁₂C₆N₆, and the charge on C is −0.72 to −0.60. The molecular orbital compositions show that the B–N bonds are the same in B₁₂N₁₂ and B₁₂C₆N₆, and the B–C bonds possess stronger covalent character. The HOMO of B₁₂C₆N₆ is formed by 2p of B and C, and the LUMO is formed by 2p of C. The energy gap of C₂₄, B₁₂N₁₂ and B₁₂C₆N₆ is 2.52, 6.84 and 3.22 eV, respectively.     

BN管状团簇到单壁纳米管的几何结构和电子性质

利用密度泛函理论(DFT),对氮化硼(BN)管状团簇的几何结构、稳定性和电子性质进行了研究.选取合适的BN结构单元作为结构生长基元,采用逐层生长的方式计算得到有限长度、不同截面尺寸的稳定管状团簇.结构中B-N交替排列,结构组成中的四元环和六元环数目均符合一般表达式.计算结果表明,通过适当组装管状团簇以及碳原子掺杂,可以制备出带隙可调的单壁氮化硼纳米管.     

Study of electronic and optical properties of pure and metal decorated boron nitride nanoribbons (B15N14H14-X): first principle calculations

Density functional theory (DFT)/time dependent density functional theory (TDDFT) based calculations were performed for basis sets 6-31G for DFT and 6-31G (d), 6-31G (d,p) and 6-31+G (d,p) for TDDFT calculations on pure boron nitride nanoribbon (BNNR) B₁₅N₁₅H₁₄ and metal decorated B₁₅N₁₄H₁₄-X BNNRs, where X = Ni⁺, Fe⁺, Co, Cr⁺, Cu and Al. The metal doping ratio = 3.45% and the doping site (nitrogen atom), were fixed for all the BNNRs. Electronic properties dipole moment, binding energy and bandgap were determined. Absorption properties in the wavelength range (100–600 nm) were studied, and optical gaps, absorption wavelengths, oscillator strengths and dominant transitions were calculated. The effect of metal doping on the electronic and optical properties was investigated. Single metal doping shifts the electronic gap of pure BNNR from insulating to semiconducting nature. Red shift in the absorption wavelengths from ultraviolet to visible in all the BNNRs was noticed.     

Carbon clusters near the step of Rh surface: implication for the initial stage of graphene nucleation

To understand the initial nucleation of graphene by chemical vapor deposition along metal step, carbon clusters (N = 1 ～ 24) near Rh (4 3 3) stepwise surface were systemically explored by first-principles calculations. Carbon chains are always more stable than carbon rings on stepped metal surface. Starting from C₆, carbon chains prefer two-end passivation on the metal step. A structural transition of carbon clusters from one-dimensional sp chains to two-dimensional s p ² networks are found at C₁₀, which corresponds to the nucleation size at a wide range of chemical potentials. According to these theoretical results, we proposed that appropriately controlling the chemical potential may be helpful for observing the four stable carbon clusters along metal step and improving the quality of graphene.