Electron-energy characteristics of double-walled carbon nanotubes doped with alkali metal atoms

A computational scheme based on density functional theory adapted for systems with translational symmetry is applied to calculating the electronic structure and energy spectrum of double-walled carbon nanotubes doped with alkali metal atoms (Li, Na, and K). The specific features of the electron-energy characteristics, including the potential curves for the interaction of nanotubes with “guest” atoms moving in the radial direction or along the circumference of the tube, are established. It is shown that doped double-walled nanotubes have an increased electron emissivity.     

Electronic structure of carbon nanotubes modified by alkali metal atoms

The electronic structure and parameters of the energy band structure of (n, 0)-type nanotubes modified by alkali metal atoms (Li, Na) and intercalated by potassium atoms are studied. The quantum-chemical semiempirical MNDO method and a model of the covalent cyclic cluster built in via ionic bonding are used to model infinitely long nanotubes. The electronic density of states of modified nanotubes is found. It is shown that semiconductor-metal transitions can occur in semiconductor nanotubes and that semimetal nanotubes can undergo metal-metal transitions.     

Stability and electronic properties of carbon nanotubes doped with transition metal impurities

We apply first-principles method to investigate the effect of the diameter on the stability and electronic properties of zigzag carbon nanotubes doped with iron, nickel and manganese impurity atoms. In this contribution we follow the evolution of the electronic and structural properties as a function of the nanotube diameter. As a general result, we found that the binding energy decreases with the increasing nanotube radius. Additionally, depending on the interaction of transition metal impurity with the tubular carbon structure, it is observed that the total magnetization varies with the tube diameter due to hybridization and confinement effects. It is also shown that such magnetization varies with the curvature radius, increasing for manganese impurity atoms and decreasing for iron and nickel.     

Interactions of transition metal atoms with He

The adiabatic interaction potentials were obtained for the paradigm transition metal-rare gas interactions: Sc(²D)-He and Ti(³F)-He and their di-cations. The ab initio approach included the coupled cluster and multireference configuration interaction methods. He atoms form very weak van der Waals complexes with Sc and Ti with well-depths of ca. 4-5 cm^-1. The interactions are characterized by the nearly-degenerate manifolds of adiabatic states with splittings of the order of 0.1 cm^-1 or less. The anisotropy of the Ti-He interaction is smaller than that for the Sc-He interaction. The origin of the weak anisotropy of these interactions was analyzed. The exchange repulsion was found to be nearly the same in the , and states due to the valence d-electrons being submerged under the doubly filled 4s electron sub-shell. The anisotropy of the total potential is controlled by the weakly-anisotropic dispersion interaction.Received: 24 September 2004, Published online: 23 November 2004PACS: 34.20.-b Interatomic and intermolecular potentials and forces, potential energy surfaces for collisions - 31.50.Df Potential energy surfaces for excited electronic states - 31.15.Ar Ab initio calculations     

Visible fluorescence induced by the metal semiconductor transition in composites of carbon nanotubes with noble metal nanoparticles

We show that single-walled carbon nanotube (SWNT) bundles emit visible fluorescence in the presence of noble metal nanoparticles and nanorods in the solid state. Conductivity measurements with metallic nanotubes, isolated from pristine SWNTs, show that they become semiconducting in the presence of the metal nanoparticles. Nanoparticle binding increases the defects in the nanotube structures which is evident in the Raman spectra. The metal-semiconductor transition removes the nonradiative decay channels of the excited states enabling visible fluorescence. Nanotube structures are imaged using this emission with resolution below the classical limits.     

Magnesium nanoparticles with transition metal decoration for hydrogen storage

We report on the hydrogen storage behaviour of Mg nanoparticles (NPs) (size range 100 nm–1 μm) with metal-oxide core–shell morphology synthesized by inert gas condensation and decorated by transition metal (TM) (Pd or Ti) clusters via in situ vacuum deposition. The structure and morphology of the as-prepared and hydrogenated NPs is studied by electron microscopy, X-ray diffraction including in situ experiments and X-ray absorption spectroscopy, in order to investigate the relationships with the hydrogen storage kinetics measured by the volumetric Sieverts method. With both Pd and Ti, the decoration deeply improves the hydrogen sorption properties: previously inert NPs exhibit complete hydrogenation with fast transformation kinetics, good stability and reversible gravimetric capacity that can attain 6 wt%. In the case of Pd-decoration, the occurrence of Mg–Pd alloying is observed at high temperatures and in dependence of the hydrogen pressure conditions. These structural transformations modify both the kinetics and thermodynamics of hydride formation, while Ti-decoration has an effect only on the kinetics. The experimental results are discussed in relation with key issues such as the amount of decoration, the heat of mixing between TM and Mg and the binding energy between TM and hydrogen.     

Strain-induced metal to semiconductor transition in ultra-small diameter single-wall carbon nanotubes

Under a large tensile strain near fracture limit, the band structures of single-wall carbon nanotubes (SWCNTs) with diameter less than 0.5 nm begin a metal to semiconductor transition and these ultra-small SWCNTs can normally maintain their metallicities. The band gap behavior of these SWCNTs intrinsically originates from the long axial direct bond lengths and the severe curvature. The gap opening comes mainly from the transfer of pπ electrons. And the localized π and σ states can result in a lower electrical conductivity. This band gap behavior suggests that it has potential to find applications in nano-electromechanical system.     

Structural,electronic and magnetic properties of the 3d transition metal atoms adsorbed on boron nitride nanotubes

Adsorption configurations for a series of transition metal (TM) 3d atoms adsorbed on the zigzag (8, 0) BNNT at five different sites have been investigated using the first-principles PAW potential within DFT under GGA. The most stable adsorption sites are different for different TM atoms. Partially filled 3d metals V, Cr and Mn can bind strongly with zigzag (8, 0) BNNT, and Sc, Ti, Co and Ni can be chemically adsorbed on the (8, 0) BNNT. The binding between the Fe or Cu atom and the BNNT is only marginal. One unusual case is Zn. Its zero binding energy independent of the adsorption sites implies it can only physically adsorbed on the BNNT mainly stemmed from the van de Waals interaction. Electronic structure analyses show that: (1) for each TM atom adsorbed at five different sites, the total DOS curves of both majority and minority spins make a slightly relative shift along the energy axis, and for each site the total DOS of the minority spin shifts slightly in high energy direction with respect to that of the majority spin lead to a exchange splitting, except fully filled 3d metals Cu and Zn; (2) total DOS curves of both the majority and minority spins for the adsorbed systems shift to the lower energy region compared with that of the pristine (8, 0) BNNT. And the smaller 3d electrons number of the TM atom, the larger shift to the lower energy region of its DOS curves; (3) for V-, Mn- and Fe-adsorbed (8, 0) BNNT, only one type of electrons (either majority spin or minority spin) passes through the Fermi level implies these adsorbed systems are all half-metals.     

稀有气体原子在纳米碳管中的周期性振荡

采用TLHT势和经典分子动力学方法研究了稀有气体原子进入单壁纳米碳管(SWCNT)的动力学过程，计算得出SWCNT能吸入稀有气体原子(He，Ne，Ar，Kr，Xe)的管径阈值r₀分别为6.3 ?，7.0 ?，8.6 ?，8.6 ?，8.6 ?，同时计算了对应的每种稀有气体原子能封装在不同管径的SWCNT中的最大初始动能E_k0.计算给出有趣的结果是封装在纳米碳管中的稀有气体原子在管中不停地作周期性振荡，振荡周期与原子进入管中的能量无关，振幅与原子进入管中的能量有关，即振幅随着入射能量的增加而增加.分析表明：给定合适类型的碳管，具有很小初始动能的稀有气体原子可在碳管中稳定的周期性振荡，其振荡频率可达GHz.     

Catalytic oxidation of carbon nanotubes with noble metal nanoparticles

Catalytic oxidation of multi-walled carbon nanotubes (MWNCTs) with some noble metal nanoparticles was observed by environmental transmission electron microscopy (E-TEM). Amoeba-like movement of the nanoparticles was observed even at a temperature of ∼400 °C, which is much lower than the melting points of any of the metals. In particular, rhodium particles reacted intensely with MWCNTs, and assumed a droplet-like shape. On the other hand, gold particles caused very little erosion of the MWCNTs under the conditions of this study.     

Field electron emission form single-walled carbon nanotubes with deposited cesium atoms

It has been found that deposition g of cesium atoms on single-walled carbon nanotubes covered with potassium atoms not only drastically increases emission current but also considerably changes the shape of current-voltage characteristics of field electron emission, namely, the characteristics become nonlinear in Fowler-Nordheim coordinates. It has been assumed that this effect is associated with the fact that field electron emission in these layers comes from single-walled carbon nanotubes, which have p-type conductivity after potassium treatment, while deposition of cesium leads to the formation of p-n junctions near nanotube tips. Part of the applied voltage drops in p-n junction, thus causing a nonlinearity of current-voltage characteristics.     

Symmetry based properties of the transition metal dichalcogenide nanotubes

The full geometrical symmetry groups (the line groups) of the monolayered, 2Hb and 3R polytypes of the inorganic MoS₂ and WS₂ micro- and nanotubes of arbitrary chirality are found. This is used to find the coordinates of the representative atoms sufficient to determine completely the geometrical structure of the tubes. Then some physical properties which can be deduced from the symmetry are discussed: electron band degeneracies, selection rules, general forms of the second rank tensors and potentials, phonon spectra. Received 13 April 2000     

Interaction of carbon monoxide with transition metal surfaces

XPS studies of the interaction of carbon monoxide with surfaces of Fe, Co and Ni indicate that at 300 K, the disproportionation reaction is prominent up to exposures of 10³ L giving rise to high surface concentrations of carbon. At higher exposures and higher temperatures, dissociation of carbon monoxide accompanied by the formation of surface oxide layers becomes more prominent. In the case of copper, disproportionation is prominent up to 10⁴ L even at 500 K followed by dissociation at higher exposures. These results are also supported by Auger spectroscopic studies.     

Atomic arrangement of iodine atoms inside single-walled carbon nanotubes

We report atomic resolution Z-contrast scanning transmission electron microscopy images that reveal the incorporation of I atoms in the form of helical chains inside single-walled carbon nanotubes. Density functional calculations and topological considerations provide a consistent interpretation of the experimental data. Charge transfer between the nanotube walls and the I chains is associated with the intercalation.     

Study on the electronic structure and hydrogen adsorption by transition metal decorated single wall carbon nanotubes

The ground state geometry and electronic structure of various 4d transition metal (TM) atom (Y, Zr, Nb and Mo) decorated single wall carbon nanotubes (SWCNTs) are obtained using density functional theory and the projector augmented wave (PAW) method. We found a systematic change in the adsorption site of the transition metal atom with increasing number of d electrons. We also predicted that Y and Zr decorated SWCNTs are metallic whereas Nb and Mo decorated SWCNTs are semiconducting. From detailed electronic structure and Bader charge analysis we found that the systematic variation of the adsorption site with the number of d electrons is related to the decreasing amount of charge transfer from the TM atom to the SWCNT along the 4d series. We have also studied the hydrogen adsorption capabilities of these decorated SWCNTs to understand the role of transition metal d electrons in binding the hydrogen molecules to the system. We found that metallic SWCNT + TM systems are better hydrogen adsorbers. We showed that the hydrogen adsorption by a TM decorated SWCNT will be maximum when all the adsorptions are physisorption and that the retention of magnetism by the system is crucial for physisorption.     

Nonlinear conductance reveals positions of carbon atoms in metallic single-wall carbon nanotubes

Nonlinear quantum conductance in finite metallic single-wall carbon nanotubes due to presence of a single defect has been studied theoretically using π-orbital tight-binding model. The correction to the conductance induced by defects is sensitively dependent on wavefunction amplitudes of contributing electronic states. It has been shown that by calculating this correction to the first order, we can delineate the position of carbon atoms on tubular surface. It can also be used to specify the SWCNT at hand and its level spacing.     

On the interaction between chemisorbed atoms at transition metal surfaces

A model hamiltonian is derived describing the interaction of two adsorbates. The nonorthogonality of the basis set is converted into a renormalization of the matrix elements. The interaction energy, direct and indirect of two hydrogen atoms and single particle spectral densities are calculated for adsorption on a semi infinite simple cubic solid. Correlation effects are included by a variational ansatz.     

Metal-to-semiconductor transition in squashed armchair carbon nanotubes

We investigate electronic transport properties of the squashed armchair carbon nanotubes, using tight-binding molecular dynamics and the Green's function method. We demonstrate a metal-to-semiconductor transition while squashing the nanotubes and a general mechanism for such a transition. It is the distinction of the two sublattices in the nanotube that opens an energy gap near the Fermi energy. We show that the transition has to be achieved by a combined effect of breaking of mirror symmetry and bond formation between the flattened faces in the squashed nanotubes.     

Peierls transition with acoustic phonons and solitwistons in carbon nanotubes

We show that the Peierls instability can result in softening of acoustic phonons with small wave vectors and suggest that this unusual transition takes place in carbon nanotubes, resulting in a static twist deformation of the nanotube lattice. The topological excitations in the ordered phase are immobile and propagate only in pairs.     

Chirality distribution and transition energies of carbon nanotubes

From resonant Raman scattering on isolated nanotubes we obtained the optical transition energies, the radial breathing mode frequency, and the Raman intensity of both metallic and semiconducting tubes. We unambiguously assigned the chiral index (n(1),n(2)) of approximately 50 nanotubes based solely on a third-neighbor tight-binding Kataura plot and find omega(RBM)=(214.4+/-2) cm(-1) nm/d+(18.7+/-2) cm(-1). In contrast to luminescence experiments we observe all chiralities including zigzag tubes. The Raman intensities have a systematic chiral-angle dependence confirming recent ab initio calculations.