Chlorine Adsorption on Graphene: Chlorographene

We perform first-principles structure optimization, phonon frequency and finite temperature molecular dynamics calculations based on density functional theory to study the interaction of chlorine atoms with graphene predicting the existence of possible chlorinated graphene derivatives. The bonding of a single chlorine atom is ionic through the transfer of charge from graphene to chlorine adatom and induces negligible local distortion in the underlying planar graphene. Different from hydrogen and fluorine adatoms, the migration of a single chlorine adatom on the surface of perfect graphene takes place almost without barrier. However, the decoration of one surface of graphene with Cl adatoms leading to various conformations cannot sustain due to strong Cl-Cl interaction resulting in the desorption through the formation of Cl$_2$ molecules. On the contrary, the fully chlorinated graphene, chlorographene CCl, where single chlorine atoms are bonded alternatingly to each carbon atom from different sides of graphene with $sp^3$-type covalent bonds, is buckled. We found that this structure is stable and is a direct band gap semiconductor, whose band gap can be tuned by applied uniform strain. Calculated phonon dispersion relation and four Raman-active modes of chlorographene are discussed.Comment: http://pubs.acs.org/doi/abs/10.1021/jp307006

Effects of static charging and exfoliation of layered crystals

Using first-principle plane wave method we investigate the effects of static charging on structural, elastic, electronic and magnetic properties of suspended, single layer graphene, graphane, fluorographene, BN and MoS2 in honeycomb structures. The limitations of periodic boundary conditions in the treatment of charged layers are clarified. Upon positive charging the band gaps between the conduction and valence bands increase, but the single layer materials become metallic owing to the Fermi level dipping below the maximum of valence band. Moreover, their bond lengths increase and their in-plane stiffness decreases. As a result, phonons are softened and frequencies of Raman active modes are lowered. High level of charging leads to instability. We showed that wide band gap BN and MoS2 slabs are metallized as a result of electron removal and their outermost layers are exfoliated once the charging exceeds a threshold value.Comment: http://link.aps.org/doi/10.1103/PhysRevB.85.04512

Elastic and plastic deformation of graphene, silicene, and boron nitride honeycomb nanoribbons under uniaxial tension: A first-principles density-functional theory study

This study of elastic and plastic deformation of graphene, silicene, and boron nitride (BN) honeycomb nanoribbons under uniaxial tension determines their elastic constants and reveals interesting features. In the course of stretching in the elastic range, the electronic and magnetic properties can be strongly modified. In particular, it is shown that the band gap of a specific armchair nanoribbon is closed under strain and highest valance and lowest conduction bands are linearized. This way, the massless Dirac fermion behavior can be attained even in a semiconducting nanoribbon. Under plastic deformation, the honeycomb structure changes irreversibly and offers a number of new structures and functionalities. Cagelike structures, even suspended atomic chains can be derived between two honeycomb flakes. Present work elaborates on the recent experiments [C. Jin, H. Lan, L. Peng, K. Suenaga, and S. Iijima, Phys. Rev. Lett. 102, 205501 (2009)] deriving carbon chains from graphene. Furthermore, the similar formations of atomic chains from BN and Si nanoribbons are predicted.Comment: http://prb.aps.org/abstract/PRB/v81/i2/e02410

Domain formation on oxidized graphene

Using first-principles calculations within density functional theory we demonstrate that the adsorption of single oxygen atom results in significant electron transfer from graphene to oxygen. This strongly disturbs the charge landscape of the C-C bonds at the proximity. Additional oxygen atoms adsorbing to graphene prefer always the C-C bonds having highest charge density and consequently they have tendency to form domain structure. While oxygen adsorption to one side of graphene ends with significant buckling, the adsorption to both sides with similar domain pattern is favored. The binding energy displays an oscillatory variation and the band gap widens with increasing oxygen coverage. While a single oxygen atom migrates over the C-C bonds on graphene surface, a repulsive interaction prevents two oxygen adatoms from forming an oxygen molecule. Our first-principles study together with finite temperature ab-initio molecular dynamics calculations concludes that oxygen adatoms on graphene cannot desorb easily without influence of external agents.Comment: under revie

Size dependence in the stabilities and electronic properties of \alpha -graphyne and its BN analogue

We predict the stabilities of \alpha-graphynes and their boron nitride analogues(\alpha-BNyne), which are considered as competitors of graphene and two-dimensional hexagonal BN. Based on first-principles plane wave method, we investigated the stability and structural transformations of these materials at different sizes using phonon dispersion calculations and ab-initio finite temperature, molecular dynamics simulations. Depending on the number of additional atoms in the edges between the corner atoms of the hexagons, n, both \alpha-graphyne(n) and \alpha-BNyne(n) are stable for even n, but unstable for odd n. \alpha-graphyne(3) undergoes a structural transformation, where the symmetry of hexagons is broken. We present the structure optimized cohesive energies, electronic, magnetic and mechanical properties of stable structures. Our calculations reveal the existence of Dirac cones in the electronic structures of \alpha-graphynes of all sizes, where the Fermi velocities decrease with increasing n. The electronic and magnetic properties of these structures are modified by hydrogenation. A single hydrogen vacancy renders a magnetic moment of one Bohr magneton. We finally present the properties of the bilayer \alpha-graphyne and \alpha-BNyne structures. We expect that these layered materials can function as frameworks in various chemical and electronic applications.Comment: Published version in The Journal of Physical Chemistr

Self-assembly mechanisms of short atomic chains on single layer graphene and boron nitride

Nucleation and growth mechanisms of short chains of carbon atoms on single-layer, hexagonal boron nitride (h-BN), and short BN chains on graphene are investigated using first-principles plane wave calculations. Our analysis starts with the adsorption of a single carbon ad-atom and examines its migrations. Once a C$_2$ nucleates on h-BN, the insertion of each additional carbon at its close proximity causes a short segment of carbon atomic chain to grow by one atom at at a time in a quaint way: The existing chain leaves its initial position and subsequently is attached from its bottom end to the top of the carbon ad-atom. The electronic, magnetic and structural properties of these chains vertically adsorbed to h-BN depend on the number of carbon atoms in the chain, such that they exhibit an even-odd disparity. An individual carbon chain can also modify the electronic structure with localized states in the wide band gap of h-BN. As a reverse situation we examined the growth of short BN atomic chains on graphene, which attribute diverse properties depending on whether B or N is the atom bound to the substrate. These results together with ab-initio molecular dynamics simulations of the growth process reveal the interesting self-assembly behavior of the grown chains. Furthermore, we find that these atomic chains enhance the chemical activity of h-BN and graphene sheets by creating active sites for the bonding of various ad-atoms and can act as pillars between two and multiple sheets of these honeycomb structures leaving wider spacing between them to achieve high capacity storage of specific molecules.Comment: Accepted for Physical Review

Nanoscale Dielectric Capacitors Composed of Graphene and Boron Nitride Layers: A First Principles Study of High-Capacitance at Nanoscale

We investigate a nanoscale dielectric capacitor model consisting of two-dimensional, hexagonal h-BN layers placed between two commensurate and metallic graphene layers using self-consistent field density functional theory. The separation of equal amounts of electric charge of different sign in different graphene layers is achieved by applying electric field perpendicular to the layers. The stored charge, energy, and the electric potential difference generated between the metallic layers are calculated from the first-principles for the relaxed structures. Predicted high-capacitance values exhibit the characteristics of supercapacitors. The capacitive behavior of the present nanoscale model is compared with that of the classical Helmholtz model, which reveals crucial quantum size effects at small separations, which in turn recede as the separation between metallic planes increases.Comment: Published version in The Journal of Physical Chemistry: http://pubs.acs.org/doi/abs/10.1021/jp403706

Structures of Fluorinated Graphenes and Their Signatures

Recent synthesis of fluorinated graphene introduced interesting stable derivatives of graphene. In particular, fluorographene (CF), namely fully fluorinated chair conformation, is found to display crucial features, such as high mechanical strength, charged surfaces, local magnetic moments due to vacancy defects and a wide band gap rapidly reducing with uniform strain. These properties, as well as structural parameters and electronic densities of states are found to scale with fluorine coverage. However, most of the experimental data reported to date neither for CF, nor for other CnF structures complies with the results obtained from first-principles calculations. In this study, we attempt to clarify the sources of disagreements.Comment: Phys. Rev. B 83, 115432 (2011