Search

Electrides are ionic compounds in which electrons behave as anions in the interior of a positively charged framework. As a layered electride, ${\mathrm{Gd}}_{2}\mathrm{C}$ receives attention because of its ferromagnetism. Although previous research has focused on the bulk properties of ${\mathrm{Gd}}_{2}\mathrm{C}$, few studies have focused on ultrathin layers or surfaces for two-dimensional (2D) characteristics. Here, we report a first-principles study of the electronic properties of few-layer ${\mathrm{Gd}}_{2}\mathrm{C}$ structures. ${\mathrm{Gd}}_{2}\mathrm{C}$ has a work function of 3.35 eV. When a layered electride is exfoliated, the interstitial layer becomes a surface and may be exposed to the outside. Because the interlayer region has changed to the surface, the properties of the electron gases once located in the interlayer in the past will also change. We found that the surface anionic electrons accounted for about 25% of the number of electrons in the interlayer region in the absence of an external electric field. When we applied an external electric field, the number of surface electrons increased, and the increase was proportional to the square of the field intensity. Since the electronic properties of 2D materials can be understood through scanning tunneling spectroscopy (STS), we also performed the STS simulations. At $\ensuremath{-}0.9\phantom{\rule{0.28em}{0ex}}\mathrm{eV}$, the STS image was blurred because of surface anionic electrons. In contrast to the spin-up electron, an interlayer band of the spin-down electron crossed the Fermi level in the ultrathin ${\mathrm{Gd}}_{2}\mathrm{C}$ layers. Our findings open a possibility that the spin-polarized electronic gas in the few-layer electride could be used for spintronics.

Using density functional theory calculations, we have studied the edge-functionalization of armchair graphene nanoribbons (AGNRs) with pentagonal-hexagonal edge structures. While the AGNRs with pentagonal-hexagonal edge structures (labeled (5,6)-AGNRs) are metallic, the edge-functionalized (5,6)-AGNRs with substitutional atoms opens a band gap. We find that the band structures of edge-functionalized (5,6)-N-AGNRs by substitution resemble those of defect-free (N-1)-AGNR at the {\Gamma} point, whereas those at the X point show the original ones of the defect-free N-AGNR. The overall electronic structures of edge-functionalized (5,6)-AGNRs depend on the number of electrons, supplied by substitutional atoms, at the edges of functionalized (5,6)-AGNRs., Comment: 12 pages, 5 figures

Detecting dopamine is of great biological importance because the molecule plays many roles in the human body. For instance, the lack of dopamine release is the cause of Parkinson's disease. Although many researchers have carried out experiments on dopamine detection using carbon nanotubes (CNTs), there are only a few theoretical studies on this topic. We study the adsorption properties of dopamine and its derivatives, L-DOPA and dopamine o-quinone, adsorbed on a semiconducting (10, 0) CNT, using density functional theory calculations. Our computational simulations reveal that localized states originating from dopamine o-quinone appear in the bandgap of the (10, 0) CNT, but those originating from dopamine and L-DOPA do not appear in the gap. Therefore, dopamine o-quinone is expected to be detectable using an external electric field but dopamine and L-DOPA should be difficult to detect., Comment: 13 pages, 5 figures

Using density functional calculations, we study atomic and electronic structures of monolayer hexagonal boron nitride (h-BN) and vertical graphene/h-BN heterostructures with substitutional carbon defects. For monolayer h-BN, a carbon atom substituted for a boron or nitrogen atom causes spin polarization. In the presence of an adjacent graphene sheet, however, the spin magnetic moment disappears owing to interlayer charge transfer for a CB defect. Interestingly, two carbon defects in a hexagon of monolayer h-BN do not induce magnetic properties. In contrast, two CB defects (two CN defects) can have spin polarization in the vertical graphene/h-BN heterostructures because of interlayer charge transfer.

We investigated the atomic and electronic structures of metal-functionalized graphene using density functional theory calculations. As dopants, Fe, Co, Ni, and Cu atoms were considered in the form of a single transition metal (TM) atom and a two-atom pair. Our results show that a single Co atom and a Co-Co pair are the most promising for graphene functionalization, compared with Fe, Ni, and Cu atoms. Among the heteronuclear pair structures, the Co-Ni pair is energetically favorable. The density of states analysis shows hybridization between the TM 3d and C or N 2p orbitals. The spin magnetic moments of the heteronuclear TM pairs may disappear or decrease, depending on which type of TM impurityis paired. As in metalloporphyrins, the structure has a lower formation energy when four nitrogen atoms are replaced as neighbors of the transition metal atom. The spin magnetic moment is found to be in the order Fe > Co > Ni > Cu, which correlates with the d-orbital filling of the metal atom. We believe that our work will shed light on the design of spintronic devices based on TM-functionalized graphene.

Direct observation of grains and boundaries is a vital factor in altering the electrical and optoelectronic properties of transition metal dichalcogenides (TMDs), that is, MoSe2 and WSe2. Here, we report visualization of grains and boundaries of chemical vapor deposition grown MoSe2 and WSe2 on silicon, using optical birefringence of two-dimensional layer covered with nematic liquid crystal (LC). An in-depth study was performed to determine the alignment orientation of LC molecules and their correlation with other grains. Interestingly, we found that alignment of liquid crystal has discrete preferential orientations. From computational simulations, higher adsorption energy for the armchair direction was found to force LC molecules to align on it, compared to that of the zigzag direction. We believe that these TMDs with three-fold symmetric alignment could be utilized for display applications.

Using first-principles calculations, we investigate an atomic impurity at the interface of a van der Waals heterostructure (vdW heterostructure) consisting of a zigzag graphene nanoribbon (ZGNR) and a hexagonal boron nitride (h-BN) sheet. To find effects of atomic intercalation on geometrical and electronic properties of the ZGNR on the h-BN sheet, various types of impurity atoms are considered. The embedded atoms are initially placed at the edge or the middle of the ZGNR located on the h-BN sheet. Our results demonstrate that most of the impurity atoms are more stable at the edge than at the middle in all cases we consider. Especially, a nickel atom has the smallest energy difference (~0.15 eV) between the two embedding positions, which means that the Ni atom is relatively easy to intercalate in the structure. Finally, we discuss magnetic properties for the vdW heterostructure with an intercalated atom.

Defect engineering in wide-gap semiconductors is important in controlling the performance of single-photon emitter devices. The effective incorporation of defects depends strongly on the ability to control their formation and location, as well as to mitigate attendant damage to the material. In this study, we combine density functional theory, molecular dyamics (MD), and kinetic Monte Carlo (KMC) simulations to study the energetics and kinetics of the silicon monovacancy ${V}_{\mathrm{Si}}$ and related defects in $4H$-SiC. We obtain the defect formation energy for ${V}_{\mathrm{Si}}$ in various charge states and use MD simulations to model the ion implantation process for creating defects. We also study the effects of high-temperature annealing on defect position and stability using KMC and analytical models. Using a larger (480-atom) supercell than previous studies, we obtain the temperature-dependent diffusivity of ${V}_{\mathrm{Si}}$ in various charge states and find significantly lower barriers to diffusion than previous estimates. In addition, we examine the recombination with interstitial Si and conversion of ${V}_{\mathrm{Si}}$ into ${\mathrm{C}}_{\mathrm{Si}}{V}_{\mathrm{C}}$ during annealing and propose methods for using strain to reduce changes in defect concentrations. Our results provide guidance for experimental efforts to control the position and density of ${V}_{\mathrm{Si}}$ defects within devices, helping to realize their potential as solid-state qubits.

Nematic liquid crystal (LC) molecules adsorbed on two dimensional materials are aligned along the crystal directions of the hexagonal lattice. It was demonstrated that short electric pulses can reorient the aligned LC molecules in the preferred armchair direction of hexagonal boron nitride (h-BN). Several states with a variety of colors were obtained by changing the direction and strength of the electric pulses. The ab initio calculations based on density functional theory was carried out to determine the favorable adsorption configurations of the LC molecules on the h-BN surface. A non-volatile display, in which pixel resolution can be determined by grains of hexagonal surface, is proposed, which can offer a pathway towards dynamic high-quality pixels with low power consumption, and could define a new paradigm for all non-volatile display applications.

Graphene, when deposited on a supporting substrate with a step edge, may be deformed in the presence of the step edges of the substrate. In this study, we have investigated a spatial variation in the local electronic structure near the step region, by performing first-principles calculations for carpetlike armchair graphene nanoribbons (C-AGNR) and two-dimensional periodic carpetlike graphene sheets (PCGS). Our results indicate no practical difference in the local density of states (LDOS) between those of flat and step regions. Interestingly, however, the PCGS shows a remarkable variation in the LDOS with an external electric field (E-field). Furthermore, we also discuss the dependence of the direction and the magnitude of the applied E-field on the spatial variation in the LDOS.

Unzipping carbon nanotubes has recently attracted interest as a promising route to synthesizing semiconducting graphene nanoribbons. Here, the band structures of O- and F-driven partially unzipped armchair carbon nanotubes (PUCNTs) are computed using the ab initio pseudopotential method. Although the model structures exhibit a similar pinhole with a length of ∼1 nm along the tube axis, the band structures differ distinctly. The O-driven PUCNT has many localized states in the valence band arising mainly from the O 2p orbitals, and preserves metallic properties. In contrast, the F-driven PUCNT shows properties of a semiconductor with a bandgap of ∼0:15 eV, and its localized states occur in the conduction band. When the unzipping process continues further, the O-driven PUCNT also shows the semiconducting behavior. & 2013 Published by Elsevier Ltd.

Using ab initio density functional calculations, we predict subatomic-resolution atomic force microscopy (AFM) and scanning tunneling microscopy (STM) images of vertical heterostructures of graphene/hexagonal boron nitride (h-BN) with an intercalated metal atom (Li, K, Cr, Mn, Co, or Cu), and study the effects of the extrinsic metal defect on the interfacial coupling. We find that the structural deformation of the graphene/h-BN layer caused by the metal defect strongly affects the AFM images, whereas orbital hybridization between the metal defect and the graphene/h-BN layer characterizes the STM images.

Rhombohedral multilayer graphene is a physical realization of the chiral two-dimensional electron gas that can host zero-line modes (ZLMs), also known as kink states, when the local ap opened by inversion symmetry breaking potential changes sign in real space. Here we study how the variations in the local stacking coordination of multilayer graphene affects the formation of the ZLMs. Our analysis indicates that the valley Hall effect develops whenever an interlayer potential difference is able to open up a band gap in stacking faulted multilayer graphene, and that ZLMs can appear at the domain walls separating two distinct regions with imperfect rhombohedral stacking configurations. Based on a tight-binding formulation with distant hopping terms between carbon atoms, we first show that topologically distinct domains characterized by the valley Chern number are separated by a metallic region connecting AA and AA$'$ stacking line in the layer translation vector space. We find that gapless states appear at the interface between the two stacking faulted domains with different layer translation or with opposite perpendicular electric field if their valley Chern numbers are different., 10 pages, 11 figures

Demonstrated herein is the optical-field-induced enhancement of the formation of a confined nanowater meniscus using a distance-regulated quartz tuning fork-atomic force microscope (QTF-AFM) with a 780 nm laser. While a pulled optical fiber tip approaches the surface, the laser is suddenly turned on and focuses on the front spot of the tip by the shape of the pulled optical fiber, which plays the role of an objective lens and induces the gathering effect of the water molecules directed to the electromagnetic-field gradient in air. This phenomenon facilitates a new boundary condition to form a long-range confined nano-scale liquid bridge between the tip and the surface. After the pulling of the optical fiber, 20-nm-thick gold was sputtered on the apex (diameter: approximately 100 nm) of the tip to guide and focus the beam on the spot. The critical power of the laser to overcome the barrier for the formation of a new boundary is 100 microW at the distance of 22 nm from the substrate.

We investigated the interactions of two aromatic amines, N,N,N′N′-tetramethyl-p-phenylenediamine (TMPD) and tetramethylpyrazine (TMP) with single-walled carbon nanotube (SWNT) networks. Adsorption and intercalation of amine molecules in bundled SWNTs is expected to modify the electronic structure of nanotubes in a similar way as has already been observed for alkali metals. Our ab initio density functional calculations demonstrate that TMPD donates electron to the nanotube and produces donor-like states below the conduction band whereas the effect of the TMP treatment is very weak. The electron transfer to the nanotubes has been supported experimentally by the XPS valence band spectra which show strongly modified spectral features. Especially an increase of the electronic density at the Fermi level upon adsorption of TMPD and TMP is clearly demonstrated. Rather intensive features between π* and σ* transitions in the NEXAFS spectrum of the pristine SWNTs attributed to the oxidized carbon functional groups are chemically modified upon adsorption of amines on the networks. This fact suggests that the aromatic amines evidently react with the defects, remove or replace oxygen species responsible for the p-type doping of SWNTs, and therefore are acting as a de-doping agent for the naturally p-type doped semiconducting SWNTs.

Electrides are ionic compounds in which electrons confined in the interstitial spaces serve as anions and are attractive owing to their exotic physical and chemical properties in terms of their low work function and efficient charge-transfer characteristics. Depending on the topology of the anionic electrons, the surface electronic structures of electrides can be significantly altered. In particular, the electronic structures of two-dimensional (2D) electride surfaces are of interest because the localized anionic electrons at the interlayer space can be naturally exposed to cleaved surfaces. In this paper, we report the electronic structure of 2D Y2C electride surface using scanning tunneling microscopy (STM) and first-principles calculations, which reveals that anionic electrons at a cleaved surface are absorbed by the surface and subsequently resurged onto the surface due to an applied electric field. We highlight that the estranged anionic electrons caused by the electric field occupy the slightly shifted crystallographic site compared with a bulk Y2C electride. We also measure the work function of the Y2C single crystal, and it shows a slightly lower value than the calculated one, which appears to be due to the electric field from the STM junction.

Here, a pyrolytically controlled antioxidizing photosynthesis coenzyme, β-Nicotinamide adenine dinucleotide, reduced dipotassium salt (NADH) for a stable n-type dopant for carbon nanotube (CNT) transistors is proposed. A strong electron transfer from NADH, mainly nicotinamide, to CNTs takes place during pyrolysis so that not only the type conversion from p-type to n-type is realized with 100% of reproducibility but also the on/off ratio of the transistor is significantly improved by increasing on-current and/or decreasing off-current. The device was stable up to a few months with negligible current changes under ambient conditions. The n-type characteristics were completely recovered to an initial doping level after reheat treatment of the device.

A field effect transistor (FET) measurement of a SWNT shows a transition from a metallic one to a p-type semiconductor after helical wrapping of DNA. Water is found to be critical to activate this metal-semiconductor transition in the SWNT-ssDNA hybrid. Raman spectroscopy confirms the same change in electrical behavior. According to our ab initio calculations, a band gap can open up in a metallic SWNT with wrapped ssDNA in the presence of water molecules due to charge transfer., Comment: 13 pages, 6 figures

We present a first-principle study of geometrical and electronic structure of hexagonal single-walled silicon nanotubes with a monovacancy or a substitutional defect. The C, Al or P atoms are chosen as substitutional impurities. It is found that the defect such as a monovacancy or a substitutional impurity results in deformation of the hexagonal single-walled silicon nanotube. In both cases, a relatively localized unoccupied state near the Fermi level occurs due to this local deformation. The difference in geometrical and electronic properties of different substitutional impurities is discussed., Comment: 5 figures

Hexagonal boron nitride sheets have been noted especially for their enhanced properties as substrates for sp2 carbon-based nanodevices. To evaluate whether such enhanced properties would remain under various realistic conditions, we investigate the structural and electronic properties of semiconducting carbon nanotubes on perfect and defective hexagonal boron nitride sheets under an external electric field as well as with a metal impurity, using density functional theory. We verify that the use of a perfect hexagonal boron nitride sheet as a substrate indeed improves the device performances of carbon nanotubes, compared with the use of conventional substrates such as SiO2. We further show that the hexagonal boron nitride even with some defects can perform better performance as a substrate. Our calculations, on the other hand, also suggest that some defective boron nitride layers with a monovacancy and a nickel impurity could bring about poor device behaviors since the imperfections impair electrical conductivity due to residual scattering under an applied electric field., 7 pages, 4 figures

Silicene, a silicon allotrope with a buckled honeycomb lattice, has been extensively studied in the search for materials with graphene-like properties. Here, we study the domain boundaries of a silicene 4 × 4 superstructure on an Ag(111) surface at the atomic resolution using scanning tunneling microscopy (STM) and spectroscopy (STS) along with density functional theory calculations. The silicene domain boundaries (β-phases) are formed at the interface between misaligned domains (α-phases) and show a bias dependence, forming protrusions or depressions as the sample bias changes. In particular, the STM topographs of the silicene–substrate system at a bias of ∼2.0 V show brightly protruding domain boundaries, which can be explained by an energy state originating from the Si 3s and 3pz orbitals. In addition, the topographs depicting the vicinity of the domain boundaries show that the structure does not follow the buckled geometry of the atomic ball-and-stick model. Inside the domain, STS data showed a step-u...

Bilayer graphene (BLG) with a tunable band gap appears interesting as an alternative to graphene for practical applications; thus, its transport properties are being actively pursued. Using density functional theory and perturbation analysis, we investigated, under an external electric field, the electronic properties of BLG in various stackings relevant to recently observed complex structures. We established the first phase diagram summarizing the stacking-dependent gap openings of BLG for a given field. Lastly, we further identified high-density midgap states, localized on grain boundaries, even under a strong field, which can considerably reduce the overall transport gap.

Among two-dimensional atomic crystals, hexagonal boron nitride (hBN) is one of the most remarkable materials to fabricate heterostructures revealing unusual properties. We perform first-principles calculations to determine whether intercalated metal atoms and vacancies can mediate interfacial coupling and influence the structural and electronic properties of the graphene/hBN heterostructure. Metal impurity atoms (Li, K, Cr, Mn, Co, and Cu) as extrinsic defects between the graphene and hBN sheets produce $n$-doped graphene. We also consider intrinsic vacancy defects and find that a boron monovacancy in hBN act as a magnetic dopant for graphene whereas a nitrogen monovacancy in hBN serves as a nonmagnetic dopant for graphene. In contrast, smallest triangular vacancy defects in hBN are unlikely to result in significant changes in the electronic transport of graphene. Our findings reveal that the hBN layer with some vacancies or metal impurities enhance the interlayer coupling in the graphene/hBN heterostructure with respect to charge doping and electron scattering., 6 figures, 7 pages

To study the binding of hydrogen molecules on Ca-inserted porphyrin, we perform ab initio pseudopotential calculations within the local density approximation (LDA). One Ca atom is inserted in the central N 4 cavity formed by the removal of two hydrogen atoms of porphin. By increasing the number of hydrogen molecules, we investigate hydrogen binding on Ca-inserted porphyrin for hydrogen storage. We find that the binding energy of H 2 molecules to the Ca atom is ∼0.25 eV/H 2 up to four hydrogen molecules. When the fifth or sixth H 2 molecule is adsorbed on the Ca atom, the molecule is adsorbed onto Ca-porphyrin with the average binding energy of ∼0.2 eV/H 2 . Examining the projected density of states, we study orbital hybridization between the Ca atom and hydrogen molecule. Finally, the possibility of Ca-porphyrin as a hydrogen storage material is discussed.

We investigate the structure and magnetic characteristics of small metal nanoclusters consisting of Gd and/or Fe within the LDA + U density-functional approach. Pure Gd and Fe nanoclusters have larger ferromagnetic moments than their respective bulk counterparts. Among binary Fe–Gd nanoclusters of dimers, trimers, and tetramers, the Fe-rich nanoclusters are energetically favored with relatively small ferromagnetic moments and the Gd-rich nanoclusters prefer antiferrimagnetic spin configurations, where Gd sites are spin up and Fe sites are spin down.

The resistivity $\ensuremath{\rho}(T)$ and magnetoresistance (MR) $(\ensuremath{\Delta}\ensuremath{\rho}/\ensuremath{\rho})$ of an entangled single-wall carbon-nanotube network are investigated. The temperature dependence of the resistivity shows a negative $d\ensuremath{\rho}/dT$ from $T=4.3--300 \mathrm{K}$ with no resistivity minimum, which is fitted well to the two-dimensional variable-range-hopping (VRH) $(\ensuremath{\rho}(T)={\ensuremath{\rho}}_{0}\mathrm{exp}[{(T}_{0}{/T)}^{1/3}])$ formula with ${T}_{0}=259.2 \mathrm{K}.$ The MR shows a negative ${H}^{2}$ behavior at low magnetic field. At $Tl~3.8 \mathrm{K}$ and high magnetic field, the negative MR becomes positive. The positive MR tends to be saturated for $Hg10 \mathrm{T}.$ The negative MR with a positive upturn can be decomposed into a positive contribution from the two-dimensional spin-dependent VRH and a negative contribution from the two-dimensional weak localization, with some contribution of the Ni impurities in the sample found with the transmission electron microscope and by energy dispersive spectrometer analysis.

Density functional theory calculations are used to investigate the electronic structures of localized states at reconstructed armchair graphene edges. We consider graphene nanoribbons with two different edge types and obtain the energy band structures and charge densities of the edge states. By examining the imaginary part of the wavevector in the forbidden energy region, we reveal the decay behavior of the wavefunctions in graphene. The complex band structures of graphene in the armchair and zigzag directions are presented in both tight-binding and first-principles frameworks., Comment: 7 pages, 7 figures

We investigate the roles of the pseudospin and the valley degeneracy in electron scattering at graphene edges. It is found that they are strongly correlated with charge density modulations of short-wavelength oscillations and slowly decaying beat patterns in the electronic density profile. Theoretical analyses using nearest-neighbor tight-binding methods and first-principles density-functional theory calculations agree well with our experimental data from scanning tunneling microscopy. The armchair edge shows almost perfect intervalley scattering with pseudospin invariance regardless of the presence of the hydrogen atom at the edge, whereas the zigzag edge only allows for intravalley scattering with the change in the pseudospin orientation. The effect of structural defects at the graphene edges is also discussed.

Electrostatic screening between carbon nanotubes (CNTs) in a small CNT bundle leads to a switching behavior induced by electric field perpendicular to the bundle axis. Using a first-principles method, we investigate the electronic structures of bundles consisting of two or three CNTs and the effects of the electric field applied perpendicular to the bundle axis. The applied field causes band gap closure in semiconducting bundles, while a gap opening occurs in metallic ones, which enables considerable modulation of bundle conductivity. The modulation effect originates from symmetry breaking due to electrostatic screening between the adjacent tube walls.

Metal atoms on graphene, when ionized, can act as a point charge impurity to probe a charge response of graphene with the Dirac cone band structure. To understand the microscopic physics of the metal-atom-induced charge and spin polarization in graphene, we present scanning tunneling spectroscopy (STS) simulations based on density functional theory calculations. We find that a Cs atom on graphene are fully ionized with a significant band bending feature in the STS, whereas the charge and magnetic states of Ba and La atoms on graphene appear to be complicated due to orbital hybridization and Coulomb interaction. By applying an external electric field, we observe changes in charge donations and spin magnetic moments of the metal adsorbates on graphene., 8 pages, 6 figures

Using first-principles calculations, we examine the electronic and magnetic properties of partially open zigzag carbon nanotube (CNT) superlattices. It is found that depending on their opening degree, these superlattices can exhibit multiple localized states around the Fermi energy. More importantly, some electronic states confined in some parts of the structure even have special magnetic orderings. We demonstrate that, as a proof of principle, some partially open zigzag CNT superlattices are by themselves giant (100%) magnetoresistive devices. Furthermore, the localized(and spin-polarized) states as well as the band gaps of the superlattices could be further modulated by external electric fields perpendicular to the tube axis, and a bias voltage along the tube axis may be used to control the conductance of two spin states. We believe that these results will open the way to the production of novel nanoscale electronic and spintronic devices., In submission

We investigated the effect of on-site Coulomb interactions on the structural and magnetic ground state of the fullerene C$_{20}$ based on density-functional-theory calculations within the local density approximation plus on-site Coulomb corrections (LDA+$U$). The total energies of the high symmetry ($I_{h}$) and distorted ($D_{3d}$) structures of C$_{20}$ were calculated for different spin configurations. The ground state configurations were found to depend on the forms of exchange-correlation potentials and the on-site Coulomb interaction parameter $U$, reflecting the subtle nature of the competition between Jahn-Teller distortion and magnetic instability in fullerene C$_{20}$. While the non-magnetic state of the distorted $D_{3d}$ structure is robust for small $U$, a magnetic ground state of the undistorted $I_{h}$ structure emerges for $U$ larger than 4 eV when the LDA exchange-correlation potential is employed., 4 figures, 1 table

Using first-principles electronic structure calculations, we show that trapping-mediated dissociative chemisorption of ${\text{H}}_{2}$ molecules may occur on boron-doped fullerenes. Employing the Polanyi--Wigner equation and the van't Hoff--Arrhenius law parameterized by the results of first-principles calculations, we find that a ${\text{H}}_{2}$ molecule adsorbed on boron-doped fullerenes can be dissociated without additional catalysts. The dissociation occurs in $\ensuremath{\sim}0.5\text{ }\text{ps}$ at room temperature, which is also supported by independent molecular dynamics simulations. Our findings indicate that boron-doped fullerenes can be used as an atomic hydrogen storage material, but not a molecular hydrogen one, at ambient conditions.

Vacancy-induced magnetism in graphene bilayers is investigated using spin-polarized density functional theory calculations. One of two graphene layers has a monovacancy. Two atomic configurations for bilayers are considered with respect to the position of the monovacancy. We find that spin magnetic moments localized at the vacancy site decreases by ~10 % for our two configurations, compared with the graphene monolayer with a monovacancy. The reduction of the spin magnetic moment in the graphene bilayers is attributed to the interlayer charge transfer from the adjacent layer to the layer with the monovacancy, compensating for spin magnetic moments originating from quasilocalized defect state., Comment: 14 pages, 1 table and 4 figures

Using the tight-binding method and the Landauer-B\"{u}ttiker conductance formalism, we demonstrate that a multiply connected armchair carbon nanotube with a mirror-reflection symmetry can sustain an electron current of the $\pi$-bonding orbital while suppress that of the $\pi$-antibonding orbital over a certain energy range. Accordingly, the system behaves like an electron orbital valve and may be used as a scanning tunneling microscope to probe pairing symmetry in d-wave superconductors or even orbital ordering in solids which is believed to occur in some transition-metal oxides., Comment: 4 figures, 12 pages

Several paired, localized gap states were observed in semiconducting single-wall carbon nanotubes using spatially resolved scanning tunneling spectroscopy. A pair of gap states is found far from the band edges, forming deep levels, while the other pair is located near the band edges, forming shallow levels. With the help of a first-principles study, the former is explained by a vacancy-adatom complex while the latter is explained by a pentagon-heptagon structure. Our experimental observation indicates that the presence of the gap states provides a means to perform local band-gap engineering as well as doping without impurity substitution.

We examine effects of encapsulated metal atoms inside a C$_{60}$ molecule on the activation energy barrier to the Stone-Wales transformation using {\it ab initio} calculations. The encapsulated metal atoms we study are K, Ca and La which nominally donate one, two and three electrons to the C$_{60}$ cage, respectively. We find that isomerization of the endohedral metallofullerene via the Stone-Wales transformation can occur more easily than that of the empty fullerene owing to the charge transfer. When K, Ca and La atoms are encapsulated inside the fullerene, the activation energy barriers are lowered by 0.30, 0.55 and 0.80 eV, respectively compared with that of the empty C$_{60}$ (7.16 eV). The lower activation energy barrier of the Stone-Wales transformation implies the higher probability of isomerization and coalescence of metallofullerenes, which require a series of Stone-Wales transformations., Comment: 13 pages, 3 figures, 1 table

We investigate the electron transport in multiply connected metallic carbon nanotubes within the Landauer-B\"{u}ttiker formalism. Quasibound states coupled to the incident $\pi^{*}$ states give rise to energy levels of different widths depending on the coupling strength. In particular, donorlike states originating from heptagonal rings are found to give a very narrow level. Interference between broad and narrow levels produces Fano-type resonant backscattering as well as resonant tunneling. Over a significantly wide energy range, almost perfect suppression of the conduction of $\pi^{*}$ electrons occurs, which may be regarded as filtering of particular electrons ($\pi$-pass filter).

Using first-principles density functional theory, we investigate the adsorption properties of chalcogen elements (oxygen and sulfur) on an anionic golden nanocage Au 16 and its effects on the structural and electronic properties of the golden cage. In particular, we find that when a sulfur atom is encapsulated inside Au 16 , its bonding character with Au atoms appears ionic due to electron transfer from sulfur to the gold nanocage. In contrast, the exohedrally adsorbed S atom tends to have strong orbital hybridization with the golden nanocage. For an oxygen adsorption case, electrons from the golden cage tend to be shared with the adsorbed O atom exhibiting strong orbital hybridization, regardless of its adsorption sites. To investigate the transition behaviors between the most stable exohedral and endohedral adsorption configurations, we calculate the activation and reaction energies in the transition. The oxygen atom experiences a lower energy barrier than the sulfur atom due to its smaller atomic radius. Finally, we explore the vibrational properties of S- or O-adsorbed Au 16 buckyballs by calculating their infrared spectra. (Some figures may appear in colour only in the online journal)

We have measured the electrical resistivity and thermoelectric power (TEP) of single wall carbon nanotube (SWCN) network. The resistivity result can be fitted to the variable range hopping (VRH) type conduction formula. The room temperature TEP is about 30~60 μV/K and the overall temperature dependence of the TEP is similar to that of the disordered alloy which shows the electron-phonon enhancement of TEP. By applying the magnetic field up to 6 Tesla, the magnitude of the TEP is reduced by ~2 μV/K while the overall temperature dependence is more or less the same. The results are discussed by the heterogeneous model which was adapted to the conducting polymers.

We study the modification in the electronic structure of the carbon nanotube induced by vacancy-related defects using the first-principles calculation. Three defect configurations which are likely to occur in semiconducting carbon nanotubes are considered. A vacancy-adatom complex is found to bring about a pair of localized states deep inside the energy gap. A pentagon-octagon-pentagon topological defect produced by the divacancy is structurally stable and gives rise to an unoccupied localized state in the gap. We also discuss the character of partially occupied localized state produced by a substitutional impurity plus a monovacancy.