Structural and electronic properties of fluorinated boron nitride nanotubes

The effects of F doping on the structural and electronic properties of the (5, 5) single-walled boron nitride nanotube (BNNT) are investigated by using the density functional theory method. The chemiadsorption of F maintains the hexagonal BN network, increases the lattice constant, and introduces acceptor impurity states. On the other hand, substitutional doping of F destroys the hexagonal BN network, decreases the lattice constant, but does not alter the insulating feature of the BNNT. The observed insulator-to-semiconducting transition, a lattice contraction, and a highly disordered atom arrangement in the sidewall of BNNTs upon F doping appear to be most reasonably attributed to a codoping of dominating substitutional F over chemiabsorbed F, which can induce deep donor impurity states, a lattice contraction, and a destruction of the hexagonal BN network simultaneously.     

Hydrogen adsorption on carbon-doped boron nitride nanotube

The adsorption of atomic and molecular hydrogen on carbon-doped boron nitride nanotubes is investigated within the ab initio density functional theory. The binding energy of adsorbed hydrogen on carbon-doped boron nitride nanotube is substantially increased when compared with hydrogen on nondoped nanotube. These results are in agreement with experimental results for boron nitride nanotubes (BNNT) where dangling bonds are present. The atomic hydrogen makes a chemical covalent bond with carbon substitution, while a physisorption occurs for the molecular hydrogen. For the H(2) molecule adsorbed on the top of a carbon atom in a boron site (BNNT + C(B)-H(2)), a donor defect level is present, while for the H(2) molecule adsorbed on the top of a carbon atom in a nitrogen site (BNNT + C(N)-H(2)), an acceptor defect level is present. The binding energies of H(2) molecules absorbed on carbon-doped boron nitride nanotubes are in the optimal range to work as a hydrogen storage medium.     

Electronic structure of octagonal boron nitride nanotubes

The effect of an octagonal lattice configuration on a boron nitride nanotube is explored using first principle calculations. Calculations show that the formational energy of an octagonal boron nitride nanotube (o‐BNNT) is an exothermic reaction. Boron and nitrogen atoms within an o‐BNNT have an average of 2.88 electrons and 9.09 electrons, respectively, indicating ionic‐like bonding. In addition, the electronic structure of the octagonal boron nitride nanotube shows semiconductive properties, while h‐BNNT is reported to be an insulator. Additional o‐BNNTs with varying diameters are calculated where the results suggest that the diameter has an effect on the binding energy and bandgap of the o‐BNNT. The defect sites of the o‐BNNT are reactive against hydrogen where a boron defect is particularly reactive. Thus, this work suggests that physical and chemical properties of a boron nitride nanotube can be tailored and tuned by controlling the lattice configuration of the nanotube.     

Vibrational and electronic properties of single-walled and double-walled boron nitride nanotubes

We calculated IR, nonresonance Raman spectra and vertical electronic transitions of the zigzag single-walled and double-walled boron nitride nanotubes ((0,n)-SWBNNTs and (0,n)@(0,2n)-DWBNNTs). In the low frequency range below 600 cm⁻¹, the calculated Raman spectra of the nanotubes showed that RBMs (radial breathing modes) are strongly diameter-dependent, and in addition the RBMs of the DWBNNTs are blue-shifted reference to their corresponding one in the Raman spectra of the isolated (0,n)-SWBNNTs. In the high frequency range above ∼1200 cm⁻¹, two proximate Raman features with symmetries of the A_1g (∼1355 ± 10 cm⁻¹) and E_2g (∼1330 ± 25 cm⁻¹) first increase in frequency then approach a constant value of ∼1365 and ∼1356 cm⁻¹, respectively, with increasing tubes’ diameter, which is in excellent agreement with experimental observations. The calculated IR spectra exhibited IR features in the range of 1200–1550 cm⁻¹ and in mid-frequency region are consistent with experiments. The calculated dipole allowed singlet–singlet and triplet–triplet electronic transitions suggesting a charge transfer process between the outer- and inner-shells of the DWBNNTs as well as, upon irradiation, the possibility of a system that can undergo internal conversion (IC) and intersystem crossing (ISC) processes, besides the photochemical and other photophysical processes.     

Effects of electric and magnetic fields on the electronic properties of zigzag carbon and boron nitride nanotubes

We have investigated the electronic properties of zigzag CNTs and BNNTs under the external transverse electric field and axial magnetic field, using tight binding approximation. It was found that after switching on the electric and magnetic fields, the band modification such as distortion of the degeneracy, change in energy dispersion, subband spacing and band gap size reduction occurs. The band gap of zigzag BNNTs decreases linearly with increasing the electric field strength but the band gap variation for CNTs increases first and later decreases (Metallic) or first hold constant and then decreases (semiconductor). For type (II) CNTs, at a weak magnetic field, by increasing the electric field strength, the band gap remains constant first and then decreases and in a stronger magnetic field the band gap reduction becomes parabolic. For type (III) CNTs, in any magnetic field, the band gap increases slowly until reaches a maximum value and then decreases linearly. Unlike to CNTs, the magnetic field has less effects on the BNNTs band gap variation.     

DFT study on the structural and electronic properties of Pt-doped boron nitride nanotubes

First-principles calculations based on density functional theory were carried out to investigate the structural and electronic properties of Pt substitution-doped boron nitride (BN) nanotubes. The electronic and structural properties were studied for substituted Pt in the boron and the nitrogen sites of the (BN) nanotube. The band gap significantly diminishes to 2.095 eV for Pt doping at the B site while the band gap diminishes to 2.231 eV for Pt doping at the N site. The band density increases in both the valence band and the conduction band after doping. The effects of the hardness and softness group 17 (halogen elements) were calculated by density functional theory (DFT).     

Nonempirical calculations of the electronic properties of new boron nitride graphyne-like nanotubes

The nonempirical density-functional tight-binding approach to band structure calculations was used to study the structural and electronic properties of new boron nitride graphyne-like nanotubes (α-BN-NT) constructed on the basis of the atomic motif of α-graphyne. All α-BN tubes were semiconductors with gap widths of 3.8–4.2 eV. The electron energy characteristics of zigzag and armchair α-BN-NTs are discussed in comparison with the known boron nitride graphite-like nanotubes. In addition, the special features of interatomic interactions in α-BN are analyzed using the nonempirical discrete variational method of density functional theory.     

Dually-functionalized boron nitride nanotubes to target glioblastoma multiforme

Boron nitride nanotubes (BNNT) were functionalized under mild conditions, using a difunctional amine, such as glycine, with one of three targeting ligands, folic acid, a nerve growth factor, or an antibody against nerve growth factor. In addition, non-fouling BNNTs were obtained by a facile and versatile, non-destructive method via controlled surface-initiated grafting of polyzwitterions. The BNNTs were loaded with a fluorescent probe for convenient imaging of glioblastoma multiforme cells treated with BNNTs. BNNTs bearing targeting factors on their outer surface demonstrated an increased efficiency of internalization in glioblastoma multiforme cells, compared to non-modified BNNTs. The degree of internalization was affected both by the nature of the ligand/agonist linked to the BNNTs surface and by the presence of serum proteins. The polyzwitterion grafts prevented the spontaneous adsorption of serum proteins on the BNNTs.     

SnO2 nanoparticle-functionalized boron nitride nanotubes

Boron nitride nanotubes (BNNTs) were synthesized by a carbon-free chemical vapor deposition method using boron and metal oxide as reactants. Then SnO(2) nanoparticles were functionalized on them via a simple wet chemistry method. Detailed transmission electron microscopy (TEM) observations reveal that SnO(2) nanoparticles may cover the tube surface or be encapsulated in tube channels. The lattice distances of both BNNT and SnO(2) have been changed due to the strong interactions between them. The band gap energy of SnO(2) particles is found enlarged due to the size effect and interaction with BNNTs.     

Perfectly dissolved boron nitride nanotubes due to polymer wrapping

We report for the first time that boron nitride nanotubes (BNNTs) may be dissolved in organic solvents by wrapping them with a polymer. Transmission electron microscopy and cathodoluminescence studies indicate the strong pi-pi interactions between BNNTs and the polymer. A band gap ranging from 5.2 to 5.5 eV was documented for the BNNTs independent of their geometrical characteristics by using ultraviolet-visible absorption experiments on composite films and thin BNNT films prepared from solutions.     

Tremendous spin-splitting effects in open boron nitride nanotubes: application to nanoscale spintronic devices

Our calculations demonstrate that the intrinsic magnetism of boron nitride nanotubes (BNNTs) can be induced by their open ends, and the resulting magnetic moment is sensitive to the chirality of BNNTs. It is found that BNNTs, a pure sp-electron system, present a tremendous spin-splitting larger than 1 eV and that B-rich-ended and N-rich-ended BNNTs exhibit "conjugate", spin-polarized, deep-gap states. Tremendous spin-splitting effects combined with considerable local spin-polarizations at the open ends make BNNTs significant for applications of nanoscale spintronics such as spin-polarized electron emitters.     

X-ray spectra and electronic structure of boron nitride in different crystallographic modifications

The electronic energy structure of boron nitride with ZnS (c-BN) and wurtzite (w-BN) type crystal lattices is calculated by the local coherent potential (LCPA) method in a multiple scattering approximation. The local partial 2p states of boron with c-BN and w-BN are compared with the boron K emission spectra in the corresponding compounds. Fine structure is first obtained in the region of the top of the valence band. Translated fromZhurnal Struktumoi Khimii, Vol. 39, No. 6, pp. 1083–1087, November–December, 1998.     

Immobilization of proteins on boron nitride nanotubes

We report for the first time that proteins are immobilized on boron nitride nanotubes. It is found that there is a natural affinity of a protein to BNNT; this means that it can be immobilized on BNNT directly, without usage of an additional coupling reagent. For the most effective immobilization, noncovalently functionalized BNNTs should be used. The effect of immobilization was studied using high-resolution transmission electron microscopy and energy dispersion spectroscopy.     

A simple approach to covalent functionalization of boron nitride nanotubes

A novel and simple method for the preparation of chemically functionalized boron nitride nanotubes (BNNTs) is presented. Thanks to a strong oxidation followed by the silanization of the surface through 3-aminopropyl-triethoxysilane (APTES), BNNTs exposing amino groups on their surface were successfully obtained. The efficacy of the procedure was assessed with EDS and XPS analyses, which demonstrated a successful functionalization of ~15% boron sites. This approach opens interesting perspectives for further modification of BNNTs with several kinds of molecules. Since, in particular, biomedical applications are envisaged, we also demonstrated in vitro biocompatibility and cellular up-take of the functionalized BNNTs.     

Bringing about matrix sparsity in linear-scaling electronic structure calculations

The performance of linear-scaling electronic structure calculations depends critically on matrix sparsity. This article gives an overview of different strategies for removal of small matrix elements, with emphasis on schemes that allow for rigorous control of errors. In particular, a novel scheme is proposed that has significantly smaller computational overhead compared with the Euclidean norm-based truncation scheme of Rubensson et al. (J Comput Chem 2009, 30, 974) while still achieving the desired asymptotic behavior required for linear scaling. Small matrix elements are removed while ensuring that the Euclidean norm of the error matrix stays below a desired value, so that the resulting error in the occupied subspace can be controlled. The efficiency of the new scheme is investigated in benchmark calculations for water clusters including up to 6523 water molecules. Furthermore, the foundation of matrix sparsity is investigated. This includes a study of the decay of matrix element magnitude with distance between basis function centers for different molecular systems and different methods. The studied methods include Hartree–Fock and density functional theory using both pure and hybrid functionals. The relation between band gap and decay properties of the density matrix is also discussed.     

Optical absorption of zigzag single walled boron nitride nanotubes in axial magnetic field

We have investigated the effect of axial magnetic field on the band structure, dipole matrix elements and absorption spectrum in different energy ranges, using tight binding approximation. It is found that magnetic field breaks the degeneracy in the band structure and creates new allowed transitions in the dipole matrix which leads to creation of new peaks in the absorption spectrum. It is found that, unlike to CNTs which show metallic–semiconductor transition, the BNNTs remain semiconductor in any magnetic field strength. By calculation the diameter dependence of peak positions, we found that the positions of three first peaks in the lower energy region (E <5.3 eV) are proportional to n⁻². In the middle energy region (7 < E < 7.5 eV) all (n, 0) zigzag BNNTs, with even and odd nanotube index, have two distinct peaks in the absence of magnetic field which these peaks may be used to identify zigzag BNNTs from other tube chiralities. For odd (even) tubes, in the middle energy region, applying the magnetic field leads to splitting of these two peaks into three (five) distinct peaks.     

Preparation and electrochemical hydrogen storage of boron nitride nanotubes

Boron nitride (BN) nanotubes were synthesized through chemical vapor deposition over a wafer made by a LaNi5/B mixture and nickel powder at 1473 K. Scanning electron microscopy, transmission electron microscopy, energy-dispersive spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy were performed to characterize the microstructure and composition of BN nanotubes. It was found that the obtained BN nanotubes were straight with a diameter of 30-50 nm and a length of up to several microns. We first verify that the BN nanotubes can storage hydrogen by means of an electrochemical method, though its capacity is low at present. The hydrogen desorption of nonelectrochemical recombination in cyclic voltammograms, which is considered as the slow reaction at BN nanotubes, suggests the possible existence of strong chemisorption of hydrogen, and it may lead to the lower discharge capacity of BN nanotubes. It is tentatively concluded that the improvement of the electrocatalytic activity by surface modification with metal or alloy would enhance the electrochemical hydrogen storage capacity of BN nanotubes.     

Disiline-doped boron nitride nanotubes: A computational study

The properties of the electronic structure of the Disiline-doped boron nitride nanotubes (Disiline-BNNTs) are investigated by a density functional theory (DFT) calculation. The structural forms are firstly optimized and the CS tensors calculated. Subsequently, the chemical-shielding isotropic (CS^I) and chemical shielding anisotropic (CS^A) parameters are found. The shielding values of boron (B) and nitrogen (N) atoms were calculated by Gauge-Including Atomic Orbital (GIAO), Continuous Set of Gauge Transformations (CSGT) and Individual Gauges for Atoms in Molecules (IGAIM) methods, using B3LYP/6-311+G*. The B3LYP level of theory with IGAIM was the best method to evaluate the theoretical chemical shifts for studied models. The results reveal a significant effect of Disiline doping on the chemical shielding tensors at the sites of those ¹¹B and ¹⁵N nuclei located in the nearest neighborhood of the Disiline-doped ring. Furthermore, the values of dipole moments and HOMO-LUMO gaps change in the Disiline-doped models in comparison with the original pristine model.     

Over 1.0 mm-long boron nitride nanotubes

Over 1.0 mm boron nitride nanotubes (BNNTs) were successfully synthesized by an optimized ball milling and annealing method. The annealing temperature of 1100 °C is crucial for the growth of the long BNNTs because at this temperature there is a fast nitrogen dissolution rate in Fe and the B/N ratio in Fe is 1. Such long BNNTs enable a reliable single tube configuration for electrical property characterization and consequently the average resistivity of the long BNNTs is determined to be 7.1 ± 0.9 × 10⁴ Ω cm. Therefore, these BNNTs are promising insulators for three dimensional microelectromechanical system.     

A near linear-scaling smooth local coupled cluster algorithm for electronic structure

We demonstrate near linear scaling of a new algorithm for computing smooth local coupled-cluster singles-doubles (LCCSD) correlation energies of quantum mechanical systems. The theory behind our approach has been described previously, [J. Subotnik and M. Head-Gordon, J. Chem. Phys. 123, 064108 (2005)], and requires appropriately multiplying standard iterative amplitude equations by a bump function, creating local amplitude equations (which are smooth according to the implicit function theorem). Here, we provide an example that this theory works in practice: we show that our algorithm leads to smooth potential energy surfaces and yields large computational savings. As an example, we apply our LCCSD approach to measure the post-MP2 correction to the energetic gap between two different alanine tetrapeptide conformations.