Formation of the icosahedral C60 fullerene via migration of single sp atoms and annihilation of sp-atom pairs.

The disappearance of sp2 structural defects during abundant fullerene isomer formation is considered within the framework of the atomistic mechanism with participation of carbon atoms with sp hybridization. The study is carried out using the example of the icosahedral C60-Ih fullerene formation from the appropriate C58-C2v fullerene with a 7-ring. In this case the studied atomistic mechanism includes the following stages: (1) insertion of single carbon atoms into the fullerene from carbon vapor as an sp-atom instead of or above a bond, (2) directional migration of the sp-atom positions towards the 7-ring with decrease of energy, and (3) meeting of two sp atoms near the 7-ring with annihilation of the sp-atom pair and formation of the sp2 structure of the C60-Ih fullerene. The probabilities of all possible sp-atom positions on the appropriate C58-C2v fullerene shell are estimated as a function of temperature using the total energies of these positions obtained by spin-polarized density functional theory calculations using the PBE functional. Based on these estimations, it is shown that formation of the C60-Ih isomer is the most probable within the framework of the considered mechanism relative to other C60 isomers. The energetics of sp-atom pair annihilation in the formation of the C60-Ih isomer is also studied via DFT calculations. The advantages of the considered atomistic mechanism of the abundant fullerene isomer formation are discussed.

Formation of carbon propeller-like molecules from starphenes under electron irradiation.

Formation of carbon propeller-like molecules (CPLMs) from starphenes on a graphene substrate under electron irradiation with about 100% yield is observed in molecular dynamics simulations using the REBO-1990EVC_CH potential and CompuTEM algorithm. A CPLM consists of three carbon atomic chains connected to the central hexagon and is formed as a result of the spontaneous breaking of bonds between zigzag atomic rows in starphene arms after hydrogen removal by electron impacts. In the absence of the substrate, the CPLM yield is slightly decreased due to sticking between forming chains, while the formation time is increased threefold. The increase of the kinetic electron energy from 45 to 80 keV has no effect on the CPLM formation. Density functional theory (DFT) calculations performed show the stability of CPLMs with respect to the formation of new bonds between carbon atoms in the chains. DFT calculations using the accurate hybrid B3LYP functional provide an insight into the electronic structure of these new molecules.

Precise graphene cutting using a catalyst at a probe tip under an electron beam.

The method of precise cutting of 2D materials by simultaneous action of a catalyst at the tip of the scanning microscope probe and an electron beam in a high-resolution transmission electron microscope is proposed and studied using atomistic simulations by the example of graphene and a nickel catalyst. Reactive molecular dynamics simulations within the Compu-TEM approach for the description of electron impact effects show that the combination of the nickel catalyst and electron irradiation is crucial for graphene cutting. Cuts with straight edges with widths of about 1-1.5 nm can be obtained. The detailed atomistic mechanism of graphene cutting is investigated via the analysis of statistics on atom ejection and bond reorganization reactions induced by the irradiation. The principal and secondary channels of atom ejection which lead to propagation of the cut are shown to be ejection of two-coordinated atoms at the cut edges bonded to the nickel tip and three-coordinated atoms from the defective graphene structure near the tip. At the same time, the ejection of two-coordinated atoms not bonded to the tip and atoms in chains at the cut edges favors smoothing of free cut edges behind the tip. A considerable difference from the atomistic mechanism of cutting a carbon nanotube via the simultaneous action of electron irradiation and nickel catalyst is discussed. The ab initio calculations performed show a decrease of the binding energy of two-coordinated carbon atoms bonded to the nickel cluster in comparison with the same cut edge in the absence of the cluster confirming that the principal channel of atom ejection is related to the cut propagation.

Reconstruction of Zigzag Graphene Edges: Energetics, Kinetics, and Residual Defects.

Ab initio calculations are performed to study consecutive reconstruction of a zigzag graphene edge. According to the obtained energy profile along the reaction pathway, the first reconstruction step, formation of the first pentagon-heptagon pair, is the slowest one, while the growth of an already nucleated reconstructed edge domain should occur steadily at a much higher rate. Domains merge into one only in 1/4 of cases when they get in contact, while in the rest of the cases, residual defects are left. Structure, energy, and magnetic properties of these defects are studied. It is found that spontaneous formation of pairs of residual defects (i.e., spontaneous domain nucleation) in the fully reconstructed edge is unlikely at temperatures below 1000 K. Using a kinetic model, we show that the average domain length is several micrometers at room temperature and it decreases exponentially upon increasing the temperature at which the reconstruction takes place.

Analysis of structural organization and interaction mechanisms of detonation nanodiamond particles in hydrosols.

Structural organization of hydrogen and oxygen functionalized nanodiamond (ND) particles in hydrosols was investigated using a cryo-TEM method. The formation of chain-like structures was observed for hydrogen functionalized NDs while oxygen functionalized NDs tend to form more compact structures. In order to understand possible interaction mechanisms between NDs in hydrosols and to explain these experimental results, first-principles calculations were performed. Charged H-terminated ND particles and particles with partially dissociated hydroxyl and carboxyl groups on the surface were investigated as models of a real ND particle in solution. For positively charged H-terminated particles, it was established that charge distribution is determined by the values of valence band maximum for the particle facets. For negatively charged oxygen functionalized particles, the charge is localized near functional groups. In both cases, interaction is determined by the interplay between Coulomb interaction and van der Waals attraction. For detailed analysis of the ND interaction, the continual model considering this interplay was developed. The results obtained with this model indicate that the formation of chain structures from linked ND particles is caused by charge separation inside the ND particle. For the H-terminated ND particles in water solution, strongly anisotropic distribution of electrostatic potential around the particles promotes formation of non-compact chain structures of particles via interaction between facets with opposite charges. This effect of charge separation is lower in the oxygen functionalized particles as the charge is localized at the uniformly distributed O-containing functional groups, thus, more compact structures can be formed. These general qualitative statements address the problem of interactions between the large number of ND particles and explain the presented cryo-TEM experimental results.

Transformation of a graphene nanoribbon into a hybrid 1D nanoobject with alternating double chains and polycyclic regions.

Molecular dynamics simulations show that a graphene nanoribbon with alternating regions which are one and three hexagons wide can transform into a hybrid 1D nanoobject with alternating double chains and polycyclic regions under electron irradiation in HRTEM. A scheme of synthesis of such a nanoribbon using Ullmann coupling and dehydrogenation reactions is proposed. The reactive REBO-1990EVC potential is adapted for simulations of carbon-hydrogen systems and is used in combination with the CompuTEM algorithm for modeling of electron irradiation effects. The atomistic mechanism of formation of the new hybrid 1D nanoobject is found to be the following. Firstly hydrogen is removed by electron impacts. Then spontaneous breaking of bonds between carbon atoms leads to the decomposition of narrow regions of the graphene nanoribbon into double chains. Simultaneously, thermally activated growth of polycyclic regions occurs. Density functional theory calculations give barriers along the growth path of polycyclic regions consistent with this mechanism. The electronic properties of the new 1D nanoobject are shown to be strongly affected by the edge magnetism and make this nanostructure promising for nanoelectronic and spintronic applications. The synthesis of the 1D nanoobject proposed here can be considered as an example of the general three-stage strategy of production of nanoobjects and macromolecules: (1) precursors are synthesized using a traditional chemical method, (2) precursors are placed in HRTEM with the electron energy that is sufficient only to remove hydrogen atoms, and (3) as a result of hydrogen removal, the precursors become unstable or metastable and transform into new nanoobjects or macromolecules.

Molecular Dynamics Study of Ternary Montmorillonite-MT2EtOH-Polyamide-6 Nanocomposite: Structural, Dynamical, and Mechanical Properties of the Interfacial Region.

In this work, we studied the structural, dynamical, and mechanical properties of the interfacial region of a ternary montmorillonite-MT2EtOH-polyamide-6 nanocomposite using molecular dynamics modeling. Through analysis of structural parameters, including the density, bond orientation, and vector to the second-neighbor orientation, we demonstrated that, in this nanocomposite, the polymer has a laminate structure and estimated the Young modulus of its different regions. The region closest to the clay surface was the hardest with an elastic modulus of more than twice that of the pure polyamide; the other regions did not exhibit as high an elastic modulus. Closest to the clay surface, the polymer chains were aligned in the direction parallel to the platelet, which appears to explain the hardening of this region. In addition, the atomic mobility was shown to differ significantly for atoms located in the interfacial space and far away from filler particles. Therefore, we can conclude that atoms near the interface are strongly constrained, whereas those far from the interface exhibit the same mobility as that of the pure polymer. All of these analyses enabled us to estimate the thickness of the interfacial region, which did not exceed 15 Å.

Formation of Nickel Clusters Wrapped in Carbon Cages: Toward New Endohedral Metallofullerene Synthesis.

Despite the high potential of endohedral metallofullerenes (EMFs) for application in biology, medicine and molecular electronics, and recent efforts in EMF synthesis, the variety of EMFs accessible by conventional synthetic methods remains limited and does not include, for example, EMFs of late transition metals. We propose a method in which EMF formation is initiated by electron irradiation in aberration-corrected high-resolution transmission electron spectroscopy (AC-HRTEM) of a metal cluster surrounded by amorphous carbon inside a carbon nanotube serving as a nanoreactor and apply this method for synthesis of nickel EMFs. The use of AC-HRTEM makes it possible not only to synthesize new, previously unattainable nanoobjects but also to study in situ the mechanism of structural transformations. Molecular dynamics simulations using the state-of-the-art approach for modeling the effect of electron irradiation are performed to rationalize the experimental observations and to link the observed processes with conditions of bulk EMF synthesis.

The atomistic mechanism of carbon nanotube cutting catalyzed by nickel under an electron beam.

The cutting of single-walled carbon nanotubes by an 80 keV electron beam catalyzed by nickel clusters is imaged in situ using aberration-corrected high-resolution transmission electron microscopy. Extensive molecular dynamics simulations within the CompuTEM approach provide insight into the mechanism of this process and demonstrate that the combination of irradiation and the nickel catalyst is crucial for the cutting process to take place. The atomistic mechanism of cutting is revealed by a detailed analysis of irradiation-induced reactions of bond reorganization and atom ejection in the vicinity of the nickel cluster, showing a highly complex interplay of different chemical transformations catalysed by the metal cluster. One of the most prevalent pathways includes three consecutive stages: formation of polyyne carbon chains from the carbon nanotube, dissociation of the carbon chains into single and pairs of adatoms adsorbed on the nickel cluster, and ejection of these adatoms leading to the cutting of the nanotube. Significant variations in the atom ejection rate are discovered depending on the process stage and nanotube diameter. The revealed mechanism and kinetic characteristics of the cutting process provide fundamental knowledge for the development of new methodologies for control and manipulation of carbon structures at the nanoscale.

AA stacking, tribological and electronic properties of double-layer graphene with krypton spacer.

Structural, energetic, and tribological characteristics of double-layer graphene with commensurate and incommensurate krypton spacers of nearly monolayer coverage are studied within the van der Waals-corrected density functional theory. It is shown that when the spacer is in the commensurate phase, the graphene layers have the AA stacking. For this phase, the barriers to relative in-plane translational and rotational motion and the shear mode frequency of the graphene layers are calculated. For the incommensurate phase, both of the barriers are found to be negligibly small. A considerable change of tunneling conductance between the graphene layers separated by the commensurate krypton spacer at their relative subangstrom displacement is revealed by the use of the Bardeen method. The possibility of nanoelectromechanical systems based on the studied tribological and electronic properties of the considered heterostructures is discussed.

Ab initio study of edge effect on relative motion of walls in carbon nanotubes.

Interwall interaction energies of double-walled nanotubes with long inner and short outer walls are calculated as functions of coordinates describing relative rotation and displacement of the walls using van der Waals corrected density functional theory. The magnitude of corrugation and the shape of the potential energy relief are found to be very sensitive to changes of the shorter wall length at subnanometer scale and atomic structure of the edges if at least one of the walls is chiral. Threshold forces required to start relative motion of the short walls and temperatures at which the transition between diffusive and free motion of the short walls takes place are estimated. The edges are also shown to provide a considerable contribution to the barrier to relative rotation of commensurate nonchiral walls. For such walls, temperatures of orientational melting, i.e., the crossover from rotational diffusion to free relative rotation, are estimated. The possibility to produce nanotube-based bolt∕nut pairs and nanobearings is discussed.

Chiral graphene nanoribbon inside a carbon nanotube: ab initio study.

The dispersion-corrected density functional theory (DFT-D) is applied for investigation of structure and electronic properties of a sulfur-terminated graphene nanoribbon (S-GNR) encapsulated in a carbon nanotube. Two mechanisms of accommodation of the GNR in the carbon nanotube, distortion of the nanotube cross-section into an elliptic shape accompanied by bending of the GNR and transformation of the GNR to a helical conformation, are analyzed. Three types of elastic distortions of the nanotube and encapsulated GNR are revealed depending on the ratio of the diameter of the nanotube cavity to the GNR width. Helical states of the GNR are shown to be stabilized by the van der Waals attraction of sulfur atoms at neighbouring edges of adjacent turns of the GNR. The results of calculations are correlated with the experimental observations for the S-GNR synthesized recently inside the carbon nanotube. The hybrid DFT calculations of band structures of zigzag GNRs terminated with different atoms demonstrate that as opposed to O- and H-GNRs, the S-GNR is metallic even when deformed inside carbon nanotubes. Possible applications of GNRs encapsulated in carbon nanotubes are discussed.

Effect of Peierls transition in armchair carbon nanotube on dynamical behaviour of encapsulated fullerene.

The changes of dynamical behaviour of a single fullerene molecule inside an armchair carbon nanotube caused by the structural Peierls transition in the nanotube are considered. The structures of the smallest C20 and Fe@C20 fullerenes are computed using the spin-polarized density functional theory. Significant changes of the barriers for motion along the nanotube axis and rotation of these fullerenes inside the (8,8) nanotube are found at the Peierls transition. It is shown that the coefficients of translational and rotational diffusions of these fullerenes inside the nanotube change by several orders of magnitude. The possibility of inverse orientational melting, i.e. with a decrease of temperature, for the systems under consideration is predicted.

Diffusion and drift of graphene flake on graphite surface.

Diffusion and drift of a graphene flake on a graphite surface are analyzed. A potential energy relief of the graphene flake is computed using ab initio and empirical calculations. Based on the analysis of this relief, different mechanisms of diffusion and drift of the graphene flake on the graphite surface are considered. A new mechanism of diffusion and drift of the flake is proposed. According to the proposed mechanism, rotational transition of the flake from commensurate to incommensurate state takes place with subsequent simultaneous rotation and translational motion until a commensurate state is reached again, and so on. Analytic expressions for the diffusion coefficient and mobility of the flake corresponding to different mechanisms are derived in wide ranges of temperatures and sizes of the flake. The molecular dynamics simulations and estimates based on ab initio and empirical calculations demonstrate that the proposed mechanism can be dominant under certain conditions. The influence of structural defects on the diffusion of the flake is examined on the basis of calculations of the potential energy relief and molecular dynamics simulations. The methods of control over the diffusion and drift of graphene components in nanoelectromechanical systems are discussed. The possibility to experimentally determine the barriers to relative motion of graphene layers based on the study of diffusion of a graphene flake is considered. The results obtained can also be applied to polycyclic aromatic molecules on graphene and should be qualitatively valid for a set of commensurate adsorbate-adsorbent systems.

Interlayer interaction and relative vibrations of bilayer graphene.

The van der Waals corrected first-principles approach (DFT-D) is for the first time applied for investigation of interlayer interaction and relative motion of graphene layers. A methodological study of the influence of parameters of calculations with the dispersion corrected and original PBE functionals on characteristics of the potential relief of the interlayer interaction energy is performed. Based on the DFT-D calculations, a new classical potential for interaction between graphene layers is developed. Molecular dynamics simulations of relative translational vibrations of graphene layers demonstrate that the choice of the classical potential considerably affects dynamic characteristics of graphene-based systems. The calculated low values of the Q-factor for these vibrations Q≈ 10-100 show that graphene should be perfect for the use in fast-responding nanorelays and nanoelectromechanical memory cells.