Constituting a part of odd electrons that are excluded from the covalent bonding, effectively unpaired electrons are posed by the singlet instability of the single-determinant broken spin-symmetry unrestricted Hartree-Fock (UBS HF) SCF solution. A correct determination of the total number of effectively unpaired electrons ND and its fraction on each atom NDA is well provided by the UBS HF solution. The NDA value is offered to be a quantifier of atomic chemical susceptibility (or equivalently, reactivity) thus highlighting targets that are the most favorable for addition reactions of any type. The approach is illustrated for two families involving fragments of arm-chair (n,n) and zigzag (m,0) single-walled nanotubes differing by length and end structure. Short and long tubes as well as tubes with capped end and open end, in the latter case, both hydrogen terminated and empty, are considered. Algorithms of the quantitative description of any length tubes are suggested.
Through magnetic linear dichroism spectroscopy, the magnetic susceptibility anisotropy of metallic single-walled carbon nanotubes has been extracted and found to be 2-4 times greater than values for semiconducting single-walled carbon nanotubes. This large anisotropy is consistent with our calculations and can be understood in terms of large orbital paramagnetism of electrons in metallic nanotubes arising from the Aharonov-Bohm-phase-induced gap opening in a parallel field. We also compare our values with previous work for semiconducting nanotubes, which confirm a break from the prediction tha…
We have shown how the interplay between the broken symmetry associated with the finite single-wall nanotubes (SWNT) and the boundary conditions affects the electronic properties of SWNTs in a profound way. For finite SWNTs (p,q) characterized by p=k+l,q=k-l,p-q=2l,l=0,1...,k, and k=1,2..., we found that the band gaps of finite SWNTs belonging to a certain k exhibit similar well-defined oscillating patterns but with diminishing amplitudes from the armchair (l=0) to the zigzag (l=k) SWNTs. These profound changes hold intiguing implications in the potential utilization of these finite NTs as the …
We present {\it ab initio} calculations of the magnetic susceptibility and of the $^{13}$C chemical shift for carbon nanotubes, both isolated and in bundles. These calculations are performed using the recently proposed gauge-including projector augmented-wave approach for the calculation of magnetic response in periodic insulating systems. We have focused on the semiconducting zigzag nanotubes with diameters ranging from 0.6 to 1.6 nm. Both the susceptibility and the isotropic shift exhibit a dependence with the diameter (D) and the chirality of the tube (although this dependence is stronger f…
High intrinsic mobility and small, biologically-compatible size make single-walled carbon nanotubes (SWNTs) in demand for the next generation of electronic devices. Further, the wide range of available bandgaps due to changes in diameter and symmetry give SWNTs greater versatility than traditional semiconductors. Single-stranded DNA has been employed to make these desirable properties accessible for large scale fabrication of devices. Because single-stranded DNA can helically wrap a SWNT, forming a stable hybrid structure, DNA/polymer wrapping has been used to disperse bundles of intrinsically…
Near-infrared magneto-optical spectroscopy of single-walled carbon nanotubes reveals two absorption peaks with an equal strength at high magnetic fields ($>$ 55 T). We show that the peak separation is determined by the Aharonov-Bohm phase due to the tube-threading magnetic flux, which breaks the time-reversal symmetry and lifts the valley degeneracy. This field-induced symmetry breaking thus overcomes the Coulomb-induced intervalley mixing which is predicted to make the lowest exciton state optically inactive (or ``dark'').
We demonstrate that in a densely packed aligned array of single walled carbon nanotubes, the breakdown of one nanotube leads to a highly correlated breakdown of neighboring nanotubes, thereby producing a nano-fissure. We show that the origin of the correlation is the electrostatic field of the broken nanotubes that produces locally inhomogeneous current and Joule heating distributions in the neighboring intact nanotubes triggering their breakdowns in the vicinity of the broken nanotubes. Our results suggest that the densely aligned array behaves like a correlated solid.
Magnetic susceptibility $χ$ of pristine and brominated arc-produced sample of multiwall carbon nanotubes was measured from 4.2 to 400 K. An additional contribution $Δχ(T)$ to diamagnetic susceptibility $χ(T)$ of carbon nanotubes was found at T $<$ 50 K for both samples. It is shown that $Δχ(T)$ are dominated by quantum correction to $χ$ for interaction electrons (interaction effects-IE). The IE shows a crossover from two-dimensional to three-dimensional at $B$ = 5.5 T. The effective interaction between electrons for interior layers of nanotubes are repulsion and the electron-electron interacti…
The formation of graphen-nanotube composites addresses a few basic problems. First, both partners are good donors and acceptors of electrons, which significantly complicates the intermolecular interaction between them leading to a two-well shape of the ground state energy term. The second problem concerns odd-electron character of the components. Similarly to high aromatics and fullerenes, much larger C-C distances provide a considerable weakening of odd electrons interaction in nanotubes and graphene that necessitates taking the configurational interaction of odd electrons into account. Avoid…
In the present work we discuss based on extensive fully atomistic molecular dynamics simulations the dynamics of Neon atoms oscillating inside (5,5)single-walled carbon nanotubes (CNTs) and boron-nitride (BNNT) ones. Our results show that sustained high frequency oscillatory regimes are possible for a large range of temperatures. Our results also show that the general features of the oscillations are quite similar to CNT and BNNT, in contrast with some speculations in previous work literature about the importance of broken symmetry and chirality exhibited by BNNTs.
The three-fold symmetry of planar boron nitride, the III-V analog to graphene, prohibits an electric polarization in its ground state, but this symmetry is broken when the sheet is wrapped to form a BN nanotube. We show that this leads to an electric polarization along the nanotube axis which is controlled by the quantum mechanical boundary conditions on its electronic states around the tube circumference. Thus the macroscopic dipole moment has an {\it intrinsically nonlocal quantum} mechanical origin from the wrapped dimension. We formulate this novel phenomenon using the Berry's phase approa…
A generalization of the Anderson model that includes pseudo-Jahn-Teller impurity coupling is proposed to describe distortions of an endohedral impurity in a carbon nanotube. Treating the distortion within mean-field theory, spontaneous axial symmetry breaking is found when the vibronic coupling strength g exceeds a critical value g$_c$. The effective potential in the symmetry-broken state is found to have O(2) symmetry, in agreement with numerical calculations. For metallic zigzag nanotubes endohedrally-doped with transition metals in the dilute limit, the low-energy properties of the system m…
We have observed a nearly fourfold increase in the electron spin resonance (ESR) signal from an ensemble of single-walled carbon nanotubes (SWCNTs) due to oxygen desorption. By performing temperature-dependent ESR spectroscopy both before and after thermal annealing, we found that the ESR in SWCNTs can be reversibly altered via the molecular oxygen content in the samples. Independent of the presence of adsorbed oxygen, a Curie-law (spin susceptibility $\propto 1/T$) is seen from $\sim$4 K to 300 K, indicating that the probed spins are finite-level species. For both the pre-annealed and post-an…
Towards the development of a useful mechanism for hydrogen storage, we have studied the hydrogenation of single-walled carbon nanotubes with atomic hydrogen using core-level photoelectron spectroscopy and x-ray absorption spectroscopy. We find that atomic hydrogen creates C-H bonds with the carbon atoms in the nanotube walls and such C-H bonds can be com-pletely broken by heating to 600 oC. We demonstrate approximately 65+/-15 at % hydrogenation of carbon atoms in the single-walled carbon nanotubes which is equivalent to 5.1+/-1.2 weight % hydrogen capacity. We also show that the hydrogenation…
The second-order nonlinear optical susceptibility ($χ_{abc}^{(2)}$) and linear electro-optical coefficient ($r_{abc}$) of a large number of single-walled zigzag, armchair and chiral SiC nanotubes (SiC-NTs) as well as bulk SiC polytypes (2H-, 4H-, 6H- and 3C-SiC) and single graphitic SiC sheet have been calculated from first-principles. The calculations are based on density functional theory in the local density approximation and highly accurate full-potential projector augmented-wave method is used. Both the zigzag and chiral SiC-NTs are found to exhibit large second-order nonlinear optical be…
Ultrafast degenerate pump-probe experiments performed on a free standing film of double walled carbon nanotubes near the first metallic transition energy of outer tube show ultrafast ($97 fs$) photobleaching followed by a photo-induced absorption with a slow relaxation of $1.8 ps$. Femtosecond closed and open aperture z-scan experiments carried out at the same excitation energy show saturation absorption and negative cubic nonlinearity. From these measurements, real and imaginary part of the third order nonlinear susceptibility are estimated to be Re($χ^{(3)}) \sim -2.2 \times 10 ^{-9} esu$ an…
Detailed analyses are made on previously published data for multi-walled carbon nanotubes. The field dependence of the Hall voltage, the temperature dependence of the Hall coefficient, and the magnetoresistance effect (Phys. Rev. Lett. 72, 697 (1994)) can all be consistently explained in terms of the coexistence of physically separated tubes and Josephson-coupled superconducting tubes with superconductivity above room temperature. The observed temperature dependencies of the remnant magnetization, the diamagnetic susceptibility, and the conductance are consistent with superconductivity above r…
Angular perturbations modify the band structure of armchair (and other metallic) carbon nanotubes by breaking the tube symmetry and may induce a metal-semiconductor transition when certain selection rules are satisfied. The symmetry requirements apply for both the nanotube and the perturbation potential, as studied within a nonorthogonal $π$-orbital tight-binding method. Perturbations of two categories are considered: an on-site electrostatic potential and a lattice deformation which changes the off-site hopping integrals. Armchair nanotubes are proved to be robust against the metal-semiconduc…
The current paper presents the second part of the study devoted to composites formed by fullerene C60 and single-walled carbon nanotube ([C60-(4,4)] carbon nanobud). The formation of composites is considered from the basic points related to the atomic chemical reactivity of the fullerene molecule and carbon nanotube. The barrier that governs the composites formation is determined in terms of the coupling energy and is expanded over two contributions that present the total energy of deformation of the composites' components and the energy of covalent coupling . The computations were performed b…
We investigate the stable structures of Fe-filled single-walled carbon nanotubes (SWNTs) on Ni(111), using density functional theory calculations. We find stable geometries and electronic states for the nanotube on Ni(111). We propose the possibility that the C-C bonds of carbon nanotube are broken by Fe wire and Ni surface. That is, when Fe-filled SWNT(3, 3) adsorb on Ni(111) surface, SWNT transforms into arch-like structure.
By using the five Angstrom diameter pores of calcined zeolite as the template, we have fabricated boron doped carbon nanotube networks via the chemical vapor deposition method. Raman data indicate the network to comprise segments of interconnected carbon nano tubes. Transport measurements showed a superconducting transition initiating at 40K, with a sharp downturn around 20K to a low resistance state at 2K, accompanied by a low resistance plateau in the current voltage characteristic, fluctuating around zero resistance. Magnetic measurements exhibited the Meissner effect characteristic of thin…
By using femtosecond laser pulses at a wavelength range from 720 to 780 nm, we have observed absorptive and refractive nonlinearities in a film of multi-walled carbon nanotubes grown mainly along the direction perpendicular to the surface of quartz substrate. The Z-scans show that both absorptive and refractive nonlinearities are of negative and cubic nature in the laser irradiance range from a few to 300 GW/cm^2. The magnitude of the third-order nonlinear susceptibility,chi-(3), is of an order of 10^-11 esu. The degenerate pump-probe measurement reveals a relaxation time of 2 ps.
The remarkable transport properties of carbon nanotubes (NTs) are determined by their unique electronic structure (1). The electronic states of a NT form one-dimensional electron and hole subbands which, in general, are separated by an energy gap (2,3). States near the energy gap are predicted to have a large orbital magnetic moment much larger than the Bohr magneton (4,5). The moment is due to electron motion around the NT circumference. This orbital magnetic moment is thought to play a role in the magnetic susceptibility of NTs (6-9) and the magneto-resistance observed in large multi-walled …
The susceptibility to delamination is one of the main concerns in fiber reinforced polymer composites (FRPs). This work demonstrates improvements of 60% in Mode-I fracture toughness after integration of thin (~30 micron), continuous veils of carbon nanotubes (CNTs) directly deposited onto carbon fiber fabric as the CNT are drawn from the gas-phase using a semi-industrial process. A combination of optical imaging, scanning electron microscopy and a Raman spectroscopy provide a new rapid tool to unambiguously determine the crack propagation path by simple visual inspection of fracture surface. T…
Using fully self-consistent thermal broken-symmetry GW we construct effective magnetic Heisenberg Hamiltonians for a series of transition metal oxides (NiO, CoO, FeO, MnO), capturing a rigorous but condensed description of the magnetic states. Then applying high-temperature expansion, we find the decomposition coefficients for spin susceptibility and specific heat. The radius of convergence of the found series determine the Neel temperature. The NiO, CoO, and FeO contain a small ferromagnetic interaction between the nearest neighbors (NN) and the dominant antiferromagnetic interaction between …
Non-equilibrium angular momentum selectivity and filtering in chiral carbon nanotubes
School of Engineering, Mackenzie Presbyterian University（麦肯锡福音大学工程学院）；MackGraphe Graphene and Nanomaterials Research Institute, Mackenzie Presbyterian University（麦肯锡福音大学MackGraphe石墨烯与纳米材料研究所）；Departamento de Física, Universidade Federal do Ceará（塞阿拉联邦大学物理系）
Healing of a hole in a carbon nanotube under electron irradiation in HRTEM at room temperature is demonstrated using molecular dynamics simulations with the CompuTEM algorithm. Formation of an amorphous patch is observed in all simulation runs. The amorphous patch is formed in the absence of external carbon adatoms only via reconstruction of the carbon bond network. It consists mainly of 5-, 6- and 7-membered rings and causes a small bottleneck. In addition, further growth of the initial amorphous patch under electron irradiation takes place. Two-coordinated atoms are found to play a crucial r…
The electron-electron interaction in carbon nanostructures was studied. A new method which allows to determine the electron-electron interaction constant $λ_c$ from the analysis of quantum correction to the magnetic susceptibility and the magnetoresistance was developed. Three types of carbon materials: arc-produced multiwalled carbon nanotubes (arc-MWNTs), CVD-produced catalytic multiwalled carbon nanotubes (c-MWNTs) and pyrolytic carbon were used for investigation. We found that $λ_c$=0.2 for arc-MWNTs (before and after bromination treatment); $λ_c$ = 0.1 for pyrolytic graphite; $λ_c >$ 0 fo…
We show that the chiral-symmetry-broken phase of massless QED in the presence of a magnetic field exhibits strong paraelectricity. A large anisotropic electric susceptibility develops in the infrared region, where most of the fermions are confined to their lowest Landau level, and dynamical mass and anomalous magnetic moment are generated via the magnetic catalysis mechanism. The nonperturbative nature of this effect is reflected in the dependence of the electric susceptibility on the fine-structure constant. The strong paraelectricity is linked to the electric dipole moments of the particle/a…
Employing a sapphire whispering gallery mode resonator, we demonstrate features of the spin-photon interaction in cavities with broken time-reflection symmetry. The broken symmetry leads to a lifting of the degeneracy between left-handed and right-handed polarised cavity photons, which results in an observable gyrotropic effect. In the high-$Q$ cavity limit, such a situation requires a modification of the Tavis-Cummings Hamiltonian to take into account conservation of spin angular momentum and the corresponding selection rules. As a result, the system is represented by a system of two linearly…
