Single-walled carbon nanotubes (SWCNTs) in their pristine form have high thermal conductivity whose further improvement has attracted a lot of interest. Some theoretical studies have suggested that the thermal conductivity of a $(10,10)$ SWCNT is dramatically enhanced by C$_{60}$ fullerene encapsulation. However, recent experiments on SWCNT bundles show that fullerene encapsulation leads to a reduction rather than an increase in thermal conductivity. Here, we employ three different molecular dynamics methods to study the influence of C$_{60}$ encapsulation on heat transport in a $(10,10)$ SWCNT. All the three methods consistently predict a reduction of the thermal conductivity of $(10,10)$ SWCNT upon C$_{60}$ encapsulation by $20\%-30\%$, in agreement with experimental results on bundles of SWCNTs. We demonstrate that there is a simulation artifact in the Green-Kubo method which gives anomalously large thermal conductivity from artificial convection. Our results show that the C$_{60}$ molecules conduct little heat compared to the outer SWCNT and reduce the phonon mean free paths of the SWCNT by inducing extra phonon scattering. We also find that the thermal conductivity of a $(10,10)$ SWCNT monotonically decreases with increasing filling ratio of C$_{60}$ molecules.
High filling of single wall carbon nanotubes (SWCNT) with C$_{60}$ and C$_{70}$ fullerenes in solvent is reported at temperatures as low as 69 $^{o}$C. A 2 hour long refluxing in n-hexane of the mixture of the fullerene and SWCNT results in a high yield of C$_{60}$,C$_{70}$@SWCNT, fullerene peapod, material. The peapod filling is characterized by TEM, Raman and electron energy loss spectroscopy and X-ray scattering. We applied the method to synthesize the temperature sensitive (N@C$_{60}$:C$_{60}$)@SWCNT as proved by electron spin resonance spectroscopy. The solvent prepared peapod samples can…
Fullerence encapsulation has been proven to be a powerful approach to enhance mechanical and electronic properties of the single-walled carbon nanotubes (SWCNTs). However, some discrepancies emerge in recent studies of the fullerence encapsulation effect on the thermal conductivity of SWCNTs. More specifically, most previous theoretical works predicted slightly enhancement of the thermal conductivity, but the recent experiment by Kodama et al. (Nat. Mat. 16, 892 (2017)) observed clear reduction of the thermal conductivity in SWCNTs by fullerence encapsulation. We perform molecular dynamics sim…
We present a paradigm in constructing very stable, faceted nanotube and fullerene structures by laterally joining nanoribbons or patches of different planar phosphorene phases. Our ab initio density functional calculations indicate that these phases may form very stable, non-planar joints. Unlike fullerenes and nanotubes obtained by deforming a single-phase planar monolayer at substantial energy penalty, we find faceted fullerenes and nanotubes to be nearly as stable as the planar single-phase monolayers. The resulting rich variety of polymorphs allows to tune the electronic properties of phos…
Graphene nanoribbons are prepared inside boron nitride nanotubes by liquid phase encapsulation and subsequent annealing of 1,2,4-trichlorobenzene. The product is imaged with high resolution transmission electron microscopy, and characterized by optical absorption and Raman spectroscopy. Carbon-containing material is detected inside the boron nitride nanotubes with energy-dispersive x-ray spectroscopy (EDS) and scanning transmission electron microscopy (STEM). The observed structures twist under the electron beam and the characteristic features of nanoribbons appear in the Raman spectra.
Recently (PRL 96, 106804 (2006)) it was suggested that cobaltocene(CC) molecules encapsulated into (7,7) carbon nanotubes (CNT@(7,7)) could be the basis for new spintronic devices. We show here based on impact molecular dynamics and DFT calculations that when dynamical aspects are explicitly considered the CC encapsulation into CNT@(7,7) does not occur, it is prevented by a dynamic barrier mainly due to van der Waals interactions. Our results show that CNT@(13,0) having enough axial space for encapsulation but no enough one to allow freely rotation of the cobaltocene molecule would be a feasib…
We present the first-principles study of effects of the charge dopants such as Cesium and Iodine encapsulated on the electronic structure of carbon nanotubes. An encapsulated cesium atom donates an electron to the nanotube and produces donor-like states below the conduction bands. In contrast, an iodine trimer (I$_{3}$) accepts an electron from the nanotube and produces an acceptor-like state above the valance band maximum. We find that a Cs atom inside a metallic armchair carbon nanotube gives rise to spatial oscillations of the density of states near the Fermi level.
Growing graphene nanoribbons from small organic molecules encapsulated in carbon nanotubes can result in products with uniform width and chirality. We propose a method based on encapsulation of 1,2,4-trichlorobenzene from the liquid phase and subsequent annealing. This procedure results in graphene nanoribbons several tens of nanometers long. The presence of nanoribbons was proven by Raman spectra both on macroscopic samples and on the nanoscale by tip-enhanced Raman scattering and high-resolution transmission electron microscopic images.
The encapsulation of hydrogen-terminated nanosized diamond fragments (the so-called diamondoids) into armchair single walled carbon nanotubes with diameters in the range of 1.0 up to 2.2 nm has been investigated using classical molecular dynamics simulations. Diameter dependent molecular ordered phases were found for the encapsulation of adamantane (C10H16), diamantane (C14H20), and dihydroxy diamantane (C14H20O2). The same types of chiral ordered phases (double, triple, 4- and 5-stranded helices) observed for the encapsulation of C60 molecules were also observed for diamondoids. On the other …
Metallocenes can be encapsulated inside the carbon nanotubes. The structural, energetic and electronic properties of organometallic MCp2@SWCNT are obtained from DFT method. We verify that such encapsulation is noncovalent functionalization, and examined binding energies and charge transfers of MCp2@(16,0)SWCNT systems. Consistent with recent experimental findings, the optimal distance between FeCp2 center and near tube-wall is 4.7 (5.1) Å for the configuration where MCp2's five-fold axis is parallel (vertical) to nanotube axis, while the minimal diameter is 9.4 (10.2) Å to exothermically encap…
Using density-functional theory calculations, we investigate the addition energy (AE) of quantum dots formed of fullerenes or closed single-wall carbon nanotubes. We focus on the connection between symmetry and oscillations in the AE spectrum. In the highly symmetric fullerenes the oscillation period is large because of the large level degeneracy and Hund's rule. For long nanotubes, the AE oscillation is fourfold. Adding defects destroys the spatial symmetry of the tubes, leaving only spin degeneracy; correspondingly, the fourfold behavior is destroyed, leaving an even/odd behavior which is qu…
We show that the magnetic properties of antiferromagnetic layered NiCl$_{2}$ can be altered under nano-sizing depending on dimensionality and morphology type of the corresponding nano-forms. By means of Monte-Carlo simulations within classical Heisenberg model, the spin ordering, magnetic part of heat capacity C$_{v}$ and Néel temperatures T$_{N}$ for multi-walled NiCl$_{2}$ nanotubes and a fullerene were calculated and analyzed in comparison with the bulk NiCl$_{2}$ and multilayered two-dimensional NiCl$_{2}$ crystals and nanostripes. We have found that the nano-structuring of NiCl$_{2}$ at t…
Endohedral Derivatives of the Recently Synthesized Two-Dimensional Fullerene Networks: Electronic and Optical Insights from First-Principles Calculations
Strong Fiber from Uniaxial Fullerene Supramolecules Aligned with Carbon Nanotubes
Aerospace Systems Directorate, Air Force Research Laboratory（航空航天系统局，美国空军研究实验室）；National Research Council（国家研究委员会）；Rice University（莱斯大学）；Air Force Research Laboratory, Materials and Manufacturing Directorate（美国空军研究实验室，材料与制造管理局）；UES, Inc.（UES公司）
We study a versatile structurally favorable periodic $sp^2$-bonded carbon atomic planar sheet with $C_{4v}$ symmetry by means of the first-principles calculations. This carbon allotrope is composed of carbon octagons and squares with two bond lengths and is thus dubbed as octagraphene. It is a semimetal with the Fermi surface consisting of one hole and one electron pocket, whose low-energy physics can be well described by a tight-binding model of $π$-electrons. Its Young's modulus, breaking strength and Poisson's ratio are obtained to be 306 $N/m$, 34.4 $N/m$ and 0.13, respectively, which are …
By sequential feeding of catalyst materials, it is revealed that the active growth sites are at the bottom of the carbon nanotubes (CNTs), and that catalyst particles are constantly encapsulated into nanotubes from the bottom. This gives a better insight into the mechanism of CNT formation and on ways to control the growth process. CNTs encapsulated with different materials should enable the study of their electronic or magnetic properties, with potential applications as building blocks for nanoelectronics and as fillers in composites for electromagenetic shielding.
New forms of carbon-based materials have received great attention, and the developed materials have found many applications in nanotechnology. Interesting novel carbon structures include the carbon peapods, which are comprised of fullerenes encapsulated within carbon nanotubes. Peapod-like nanostructures have been successfully synthesized, and have been used in optical modulation devices, transistors, solar cells, and in other devices. However, the mechanical properties of these structures are not completely elucidated. In this work, we investigated, using fully atomistic molecular dynamics si…
The hollow inside of single-wall carbon nanotubes (SWCNT) provides a unique degree of freedom to investigate chemical reactions inside this confined environment and to study the tube properties. It is reviewed herein, how encapsulating fullerenes, magnetic fullerenes, $^{13}$C isotope enriched fullerenes and organic solvents inside SWCNTs enables to yield unprecedented insight into their electronic, optical, and interfacial properties and to study their growth. Encapsulated C$_{60}$ fullerenes are transformed to inner tubes by a high temperature annealing. The unique, low defect concentration …
In this work, a novel electrospun conductive polymer nanocomposite made of polycaprolactone with an exohedral complex made of multiwalled carbon nanotubes and fullerene C60 was prepared and characterized. The preparation was straightforward and the complexes self-assembled within the nanocomposite fibers. The nanocomposite showed electrical switching behavior due to charge accumulation of fullerene C60 upon electrical stimulation. Write-once read-many memory devices were fabricated by electrospinning a nanocomposite with 0.8%wt. fullerene C60 onto interdigitated coplanar electrodes. The device…
Semiclassical description, based on electrostatics and Thomas-Fermi model is applied here to calculate dimensions of the electronic shell of a fullerene molecule and a nanotube. The internal radius of the electronic shell of a fullerene molecule, calculated within the framework of the model is 0.2808 nm. The external radius is 0.4182 nm. The experimental values are 0.279 nm and 0.429 nm correspondingly. This shows that semiclassical approach provides rather good description of the dimensions of the electronic shell in a fullerene molecule. Two types of dipole oscillations in a fullerene molecu…
Can C60 layer cover a surface of single-wall carbon nanotube (SWCNT) forming an exohedral pure-carbon hybrid with only VdW interactions? The paper addresses this question and demonstrates that the fullerene shell layer in such a bucky-corn structure can be stable. Theoretical study of structure, stability and electronic properties of the following bucky-corn hybrids is reported: C60 and C70 molecules on an individual SWCNT, C60 dimers on an individual SWCNT as well C60 molecules on SWNT bundles. The geometry and total energies of the bucky-corns were calculated by the molecular dynamics method…
We report density functional study of alternate fullerene-like cage structures and finite closed capped single-wall nanotubes of aluminum nitride. The cages and nanotubes studied are modeled as Al24N24, Al28N28, Al32N32, Al36N36, Al48N48, and Al96N96. The structure optimization and calculation of the electronic structure, vertical ionization potential, and the electron affinity are performed at the all electron level by the analytic Slater-Roothaan method, using polarized Gaussian basis set of double zeta quality. All structures are energetically stable with binding energy of about 10-11 eV pe…
Comparative Evaluation of Encapsulation Methods for Endohedral Doping of Single-Wall Carbon Nanotubes
University of Antwerp（安特卫普大学）；CASCH Center of Excellence, University of Antwerp（安特卫普大学 CASCH 卓越中心）；Institute of Nanotechnology, Karlsruhe Institute of Technology（卡尔斯鲁厄理工学院纳米技术研究所）；Claude Bernard University Lyon 1（里昂第一大学克劳德·贝尔纳大学）；Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and BIST（加泰罗尼亚纳米科学和纳米技术研究所（ICN2），西班牙国家研究委员会和巴塞罗那自治大学）；Tokyo Metropolitan University（东京都立大学）
We report the filling of single walled carbon nanotubes with an electron spin-active fullerene species where a nitroxide radical is functionalized on the fullerene cage. High resolution transmission electron microscopy (HRTEM), optical absorption and electron spin resonance (ESR) are used to determine the rotational behavior of the encapsulated molecules and determine the polar nature of the nanotube interior.
We have calculated electron spin interactions in chains of Sc@C82 endohedral fullerenes in isolation and inserted into a semiconducting or metallic single-walled carbon nanotube to form a peapod. Using hybrid density functional theory (DFT), we find that the spin resides mainly on the fullerene cage, whether or not the fullerenes are in a nanotube. The spin interactions decay exponentially with fullerene separation, and the system can be described by a simple antiferromagnetic Heisenberg spin chain. A generalised Hubbard-Anderson model gives an exchange parameter J and a Coulomb parameter U in…
The structure of MX3 transition metal trichalcogenides (TMTs, with M a transition metal and X a chalcogen) is typified by one-dimensional (1D) chains weakly bound together via van der Waals interactions. This structural motif is common across a range of M and X atoms (e.g. NbSe3, HfTe3, TaS3), but not all M and X combinations are stable. We report here that three new members of the MX3 family which are not stable in bulk, specifically NbTe3, VTe3, and TiTe3, can be synthesized in the few- to single-chain limit via nano-confined growth within the stabilizing cavity of multi-walled carbon nanotu…
We find that introducing segmented isotopic disorder patterns may considerably reduce the thermal conductivity of pristine carbon nanotubes below the uncorrelated disorder value. This is a result of the interplay between different length scales in the phonon scattering process. We use ab-initio atomistic Green's function calculations to quantify the effect of various types of segmentation similar to that experimentally produced by coalescence of isotope-engineered fullerenes.
Double-walled carbon nanotubes (DWCNTs) combined the advantages of multi-walled (MW-) and single-walled (SW-) CNTs can be obtained by transforming the precursors (e.g. fullerene, ferrocene) into thin inner CNTs inside SWCNTs as templates. However, this method is limited since the DWCNT yield is strongly influenced by the filling efficiency (depending on the type of the filled molecules), opening and cutting the SWCNTs, and the diameter of the host SWCNTs. Therefore, it cannot be applied to all types of SWCNT templates. Here we show a universal route to synthesize ultra-thin DWCNTs via making S…
The electronic states of capped semi-infinite nanotubes are studied within the phenomenological gauge field-theory model. A single manifold for the description of both the nanotube and the cap region (considered as nearly a half of either Ih or I fullerene) is suggested. The wavefunctions and the density of states (DoS) are numerically calculated for both metallic and semiconducting nanotubes. The smoothing of van Hove singularities is found and proven analytically. The comparison with the experimental observations is discussed.
Metal catalysts supporting the growth of Single Wall Carbon Nanotubes display different carbon solubilities and chemical reactivities. In order to specifically assess the role of carbon solubility, we take advantage of the physical transparency of a tight binding model established for Ni-C alloys, to develop metal carbon models where all properties, except carbon solubility, are similar. These models are used to analyze carbon incorporation mechanisms, modifications of metal / carbon wall interfacial properties induced thereby, and the associated nanotube growth mechanisms. Fine tuning carbon …
Filling of single-wall carbon nanotubes with C59N azafullerene derivatives is reported from toluene solvent at ambient temperature. The filling is characterized by high resolution transmission electron microscopy and Raman spectroscopy. The filling efficiency is the same as for C60 fullerenes and the tube-azafullerene interaction is similar to the tube-C60 interaction. Vacuum annealing of the encapsulated azafullerene results in the growth of inner tubes, however no spectroscopic signature of nitrogen built in the inner walls is detected.
We studied the temperature stability of the endohedral fullerene molecule, N@C60, inside single-wall carbon nanotubes using electron spin resonance spectroscopy. We found that the nitrogen escapes at higher temperatures in the encapsulated material as compared to its pristine, crystalline form. The temperature dependent spin-lattice relaxation time, T_1, of the encapsulated molecule is significantly shorter than that of the crystalline material, which is explained by the interaction of the nitrogen spin with the conduction electrons of the nanotubes.
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…
A novel method is presented which allows the characterization of diameter selective phenomena in SWCNTs. It is based on the transformation of fullerene peapod materials into double-wall carbon nanotubes and studying the diameter distribution of the latter. The method is demonstrated for the diameter selective healing of nanotube defects and yield from C$_{70}$ peapod samples. Openings on small diameter nanotubes are closed first. The yield of very small diameter inner nanotubes from C$_{70}$ peapods is demonstrated. This challenges the theoretical models of inner nanotube formation. An anomalo…
There is increasing attention to chemical applications of transmission electron microscopy, which is often plagued by radiation damage. The damage in organic matter predominantly occurs via ionization (radiolysis). Although radiolysis is highly important, previous studies on radiolysis have largely been descriptive and qualitative, lacking in such fundamental information as the product structure, the influence of the energy of the electrons, and the reaction kinetics. We need a chemically well-defined system to obtain such data, and have chosen as a model a variable-temperature and variable-vo…
We report on single-wall carbon nanotube (SWCNT) specific $^{13}$C isotope enrichment. The high temperature annealing of isotope enriched fullerenes encapsulated in SWCNTs yields double-wall carbon nanotubes (DWCNTs) with a high isotope enrichment of the inner wall. The vibrational spectra evidences that no carbon exchange occurs between the two walls. The method facilitates the identification of the Raman signal of the outer and inner tubes. Nuclear magnetic resonance proves the significant contrast of the isotope enriched SWCNTs as compared to other carbon phases, and provides information on…
We investigate the symmetry of the boron buckyball and a related boron nanotube. Using large-scale ab-initio calculations up to second-order Møller Plesset perturbation theory, we have determined unambiguously the equilibrium geometry/symmetry of two structurally related boron clusters: the B80 fullerene and the finite-length (5,0) boron nanotube. The B80 cluster was found to have the same symmetry, Ih, as the C60 molecule since its 20 additional boron atoms are located exactly at the centers of the 20 hexagons. Additionally, we also show that the (5,0) boron nanotube does not suffer from atom…
Optimized growth of Single Wall Carbon Nanotubes requires a full knowledge of the actual state of the catalyst nanoparticle and its interface with the tube. Using Tight Binding based atomistic computer simulations, we calculate carbon adsorption isotherms on nanoparticles of nickel, a typical catalyst, and show that carbon solubility increases for smaller nanoparticles that are either molten or surface molten under experimental conditions. Increasing carbon content favors the dewetting of Ni nanoparticles with respect to sp2 carbon walls, a necessary property to limit catalyst encapsulation an…
We compare Raman spectra from aqueous suspensions of length-separated single-walled carbon nanotubes (SWCNTs) dispersed using either polymer adsorption of single-stranded DNA or miscelle encapsulation with sodium deoxycholate surfactant. The Raman spectral features, other than the D-band, increase monotonically with nanotube length in both dispersion schemes. The intensity ratio of the disorder-induced D to G' Raman bands decays as a function of SWCNT length, proportional to 1/L, as expected for endcap defects. While the UV-vis absorption and fluorescence also increase with length for both dis…
We use an atom-atom potential between carbon atoms to obtain an interaction potential between nanotubes (assumed rigid), thereby calculating the cohesive energy of a bunch of nanotubes in hexagonal two dimensional packing. The model proposed is quite similar to our earlier work on fullerenes and organic molecular crystals. The results for inter-nanotube distances, energy per unit length, bulk modulus and phonons for inter-nanotube vibrations are obtained and compared with available data from measurements and other available calculations. We also model formation of multi-wall nanotubes. We find…
Exploring the synthesis of novel molecular nanostructures has been in the forefront of material research in the last decade. One of the most interesting nanostructures are single wall carbon nanotubes (SWCNTs). Their catalyst free growth, however, remains an elusive goal. Here, we present the growth of single wall carbon nanotubes from organic solvents such as benzene and toluene in a confined environment, inside a host SWCNT. The solvents encapsulated in SWCNTs are transformed to an inner tube when subject to a heat treatment under dynamic vacuum at 1270 $^{\circ}$C. We used isotope labeling …
The response of fullerenes and carbon nanotubes is investigated by representing each carbon atom by its atomic polarizability. The polarization of each carbon atom produces an induced dipole that is the result of the interaction with a given external field plus the mutual interaction among carbon atoms. The polarizability is obtained from the dielectric function of graphite after invoking the Clausius-Mossotti relation. This formalism is applied to the simulation of electron energy loss spectra both in fullerenes and in carbon nanotubes. The case of broad electron beams is considered and the l…
Fullerene coalescence experimentally found in fullerene-embedded single-wall nanotubes under electron-beam irradiation or heat treatment is simulated by minimizing the classical action for many atom systems. The dynamical trajectory for forming a (5,5) C$_{120}$ nanocapsule from two C$_{60}$ fullerene molecules consists of thermal motions around potential basins and ten successive Stone-Wales-type bond rotations after the initial cage-opening process for which energy cost is about 8 eV. Dynamical paths for forming large-diameter nanocapsules with (10,0), (6,6), and (12,0) chiral indexes have m…
The inclusion and encapsulation of terthiophene (T3) molecules inside zigzag single-walled carbon nanotubes (CNTs) is addressed by density functional calculations. We consider the T3 molecule inside five semiconducting CNTs with diameters ranging from 9.6 to 12.7 Ang. Our results show that the T3 inclusion process is exothermic for CNTs with diameters larger than 9.5 Ang. The highest energy gain is found to be of 2 eV, decreasing as the CNT diameter increases. This notable effect of stabilization is attributed to the positively charged CNT inner space, as induced by its curvature, which is abl…
In the present work, different synthesis procedures have been demonstrated to fill carbon nanotubes (CNTs) with $\mathrm{Fe}_{1-x}\mathrm{Ni}_x$ alloy nanoparticles (x = 0.33, 0.5). CNTs act as templates for the encapsulation of magnetic nanoparticles, and provide a protective shield against oxidation as well as prevent nanoparticles agglomeration. By variation of the reaction parameters, the purity of the samples, degree of filling, the composition and size of filling nanoparticles have been tailored and therefore the magnetic properties. The samples were analyzed by scanning electron microsc…
Graphene nanoribbons with sub-nanometer widths are extremely interesting for nanoscale electronics and devices as they combine the unusual transport properties of graphene with the opening of a band gap due to quantum confinement in the lateral dimension. Strong research efforts are presently paid to grow such nanoribbons. Here we show the synthesis of 6- and 7-armchair graphene nanoribbons, with widths of 0.61 and 0.74 nm, and excitonic gaps of 1.83 and 2.18 eV, by high-temperature vacuum annealing of ferrocene molecules inside single-walled carbon nanotubes. The encapsulation of the so-obtai…
The inability to synthesize single-wall carbon nanotubes (SWCNTs) possessing uniform electronic properties and chirality represents the major impediment to their widespread applications. Recently, there is growing interest to explore and synthesize well-defined carbon nanostructures, including fullerenes, short nanotubes, and sidewalls of nanotubes, aiming for controlled synthesis of SWCNTs. One noticeable advantage of such processes is that no metal catalysts are used, and the produced nanotubes will be free of metal contamination. Many of these methods, however, suffer shortcomings of either…
We investigate the motion of a nano tippe top, which is formed from a C60 fullerene, and which is assumed to be spinning on either a graphene sheet or the interior of a single-walled carbon nanotube. We assume no specific geometric configuration for the top, however for example, the nano tippe top might be formed by joining a fullerene C60 with a small segment of a smaller radius carbon nanotube. We assume that it is spinning on a graphene sheet or a carbon nanotube surface only as a means of positioning and isolating the device, and the only effect of the graphene or the carbon nanotube surfa…
The electrical conductivity of metallic carbon nanotubes (CNTs) quickly saturates with respect to bias voltage due to scattering from a large population of optical phonons. Decay of these dominant scatterers in pristine CNTs is too slow to offset an increased generation rate at high voltage bias. We demonstrate from first principles that encapsulation of 1D atomic chains within a single-walled CNT can enhance decay of "hot" phonons by providing additional channels for thermalisation. Pacification of the phonon population growth reduces electrical resistivity of metallic CNTs by 51% for an exam…
Present paper is a review of results, obtained in the framework of semiclassical approach in nanophysics. Semiclassical description, based on Electrostatics and Thomas-Fermi model was applied to calculate dimensions of the electronic shell of a fullerene molecule and a carbon nanotube. This simplified approach yields surprisingly accurate results in some cases. Semiclassical approach provides rather good description of the dimensions of the electronic shell of a fullerene molecule. Two types of dipole oscillations in a fullerene molecule were considered and their frequencies were calculated. S…
We have investigated the electronic properties of a C_60 molecule in between carbon nanotube leads. This problem has been tackled within a quantum chemical treatment utilizing a density functional theory-based LCAO approach combined with the Landauer formalism. Owing to low-dimensionality, electron transport is very sensitive to the strength and geometry of interfacial bonds. Molecular contact between interfacial atoms and electrodes gives rise to a complex conductance dependence on the electron energy exhibiting spectral features of both the molecule and electrodes. These are attributed to th…
Ability to encapsulate molecules is one of the outstanding features of nanotubes. The encapsulation alters physical and chemical properties of both nanotubes and guest species. The latter normally form a separate phase, exhibiting drastically different behavior compared to bulk. Ionic liquids (ILs) and apolar carbon nanotubes (CNTs) are disparate objects; nevertheless, their interaction leads to spontaneous CNT filling with ILs. Moreover, ionic diffusion of highly viscous ILs can increase 5-fold inside CNTs, approaching that of molecular liquids, even though the confined IL phase still contain…
We study the photoabsorption properties of photoactive bulk polymer/ fullerene/nanotube heterojunctions in the near-infrared region. By combining pump-probe spectroscopy and linear response time-dependent density functional theory within the random phase approximation (TDDFT-RPA) we elucidate the excited state dynamics of the $E_{11}$ transition within (6,5) and (7,5) single-walled carbon nanotubes (SWNTs) and combined with poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl-C$_{61}$-butyric acid methyl ester (PCBM) in P3HT/PCBM/SWNT blended samples. We find the presence of a photoinduced …
The stabilization of carbon nanotubes via the filling with inner tubes is demonstrated by probing the optical transitions in double-walled carbon nanotube bundles under hydrostatic pressure with optical spectroscopy. Double-walled carbon nanotube films were prepared from fullerene peapods and characterized by HRTEM and optical spectroscopy. In comparison to single-walled carbon nanotubes, the pressure-induced redshifts of the optical transitions in the outer tubes are significantly smaller below $\sim$10 GPa, demonstrating the enhanced mechanical stability due to the inner tube already at low …
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…
A 1 $μ$m long, field emitting, (5,5) single-walled, carbon nanotube (SWCNT) closed with a fullerene cap, and a similar open nanotube with hydrogen-atom termination, have been simulated using the MNDO (Modified Neglect of Diatomic Overlap) quantum-mechanical method. Both contain about 80 000 atoms. It is found that field penetration and band-bending, and various forms of chemically and electrically induced apex dipole, play roles. Field penetration may help to explain electroluminescence associated with field emitting carbon nanotubes. Charge-density oscillations, induced by the hydrogen adsorp…
We investigate a new generation of fullerene nano-oscillators: a single-walled carbon nanotube with one buckyball inside with an operating frequency in the tens-of-gigahertz range. A quantitative characterization of energy dissipation channels in the peapod pair has been performed via molecular dynamics simulation. Edge effects are found to the dominant cause of dynamic friction in the carbon-peapod oscillators. A comparative study on energy dissipation also reveals significant impact of temperature and impulse velocity on the frictional force.
In the last three decades, zero-dimensional, one-dimensional, and two-dimensional carbon nanomaterials (i.e., fullerenes, carbon nanotubes, and graphene, respectively) have attracted significant attention from the scientific community due to their unique electronic, optical, thermal, mechanical, and chemical properties. While early work showed that these properties could enable high performance in selected applications, issues surrounding structural inhomogeneity and imprecise assembly have impeded robust and reliable implementation of carbon nanomaterials in widespread technologies. However, …
