arXiv subjects

J. A. Verges

Publications and source records attributed to J. A. Verges.

At least 19 recordsLinked to original sources

arXiv2019

Electron enrichment of zigzag edges of armchair-oriented graphene nano-ribbons increases their stability and induces pinning of Fermi level

Zigzag edges of neutral armchair-oriented Graphene Nano-Ribbons show states strongly localized at those edges. They behave as free radicals that can capture electrons during processing, increasing ribbon's stability. Thus, charging and its consequences should be investigated.Total energy calculations of finite ribbons using spin polarized Density Functional Theory (DFT) show that ribbon's charging is feasible. Energies for Pariser-Parr-Pople (PPP) model Hamiltonian are compatible with DFT allowing the study of larger systems. Results for neutral ribbons indicate: i) the fundamental gap of spin polarized (non polarized) solutions is larger (smaller) than experimental data, ii) the ground state is spin polarized, a characteristic still not observed experimentally. Total energy of GNRs decreases with the number of captured electrons reaching a minimum for a number that mainly depends on zigzag edges size. The following changes with respect to neutral GNRs are noted: i) the ground state is not spin polarized, ii) fundamental gap is in-between that of spin polarized and non polarized solutions of neutral ribbons, iii) while in neutral ribbons valence and conduction band onsets vs. the fundamental gap, linearly and symmetrically approach mid-gap with slope 0.5, charging induces Fermi level pinning, i.e., the slopes of the valence and conduction bands being about 0.1 and 0.9, in agreement with experiment.

cond-mat.mes-hall↗

arXiv2014

The role of potassium orbitals in the metallic behavior of K3picene

Detailed electronic structure calculations of picene clusters doped by potassium modeling the crystalline K3picene structure show that while two electrons are completely transferred from potassium atoms to the LUMO of pristine picene, the third one remains closely attached to both material components. Multiconfigurational analysis is necessary to show that many structures of almost degenerate total energies compete to define the cluster ground state. Our results prove that the 4s orbital of potassium should be included in any interaction model describing the material. We propose a quarter filled two orbital model as the most simple model capable of describing the electronic structure of K-intercalated picene. Precise solutions obtained by a development of Lanczos method show low energy electronic excitations involving orbitals located at different positions. Consequently, metallic transport is possible in spite of the clear dominance of interaction over hopping.

cond-mat.str-el↗

arXiv2011

Ab initio electronic and geometrical structures of tripotassium-intercalated phenanthrene

The geometrical and electronic structure of tripotassium doped phenanthrene, \ce{K3C14H10}, have been studied by first-principles density functional theory. The main effect of potassium doping is to inject charge in the narrow phenanthrene conduction band, rendering the system metallic. The Fermi surface for the experimental X-rays unit cell is composed of two sheets with marked one and two dimensional character respectively.

cond-mat.mtrl-sci↗

arXiv2011

Crystal structure and electronic states of tripotassium picene

The crystal structure of potassium doped picene with an exact stoichiometry (K3C22H14, K3picene from here onwards) has been theoretically determined within Density Functional Theory allowing complete variational freedom of the crystal structure parameters and the molecular atomic positions. A modified herringbone lattice is obtained in which potassium atoms are intercalated between two paired picene molecules displaying the two possible orientations in the crystal.Along the c-axis, organic molecules alternate with chains formed by three potassium atoms. The electronic structureof the doped material resembles pristine picene, except that now the bottom of the conduction band is occupied by six electrons coming from the ionized K atoms (six per unit cell). Wavefunctions remain based mainly on picene molecular orbitals getting their dispersion from intralayer edge to face CH/pi bonding, while eigenenergies have been modified by the change in the electrostatic potential. The small dispersion along the c-axis is assigned to small H-H overlap. From the calculated electronic density of states we expect metallic behavior for potassium doped picene.

cond-mat.mtrl-sci↗

arXiv2011

Electronic and Geometrical Structure of Potassium doped Phenanthrene

The geometrical and electronic structure of potassium doped phenanthrene, \ce{K3C14H10}, have been studied by first-principles density functional theory. The main effect of potassium doping is to inject charge in the narrow phenanthrene conduction band, rendering the system metallic. The Fermi surface for the experimental X-rays structure is composed of two sheets with marked one and two dimensional character respectively.

cond-mat.mtrl-sci↗

arXiv2011

Hydrogen on graphene under stress: Molecular dissociation and gap opening

Density functional calculations are employed to study the molecular dissociation of hydrogen on graphene, the diffusion of chemisorbed atomic species, and the electronic properties of the resulting hydrogen on graphene system. Our results show that applying stress to the graphene substrate can lower the barrier to dissociation of molecular hydrogen by a factor of six, and change the process from endothermic to exothermic. These values for the barrier and the heat of reaction, unlike the zero stress values, are compatible with the time scales observed in experiments. Diffusion, on the other hand, is not greatly modified by stress. We analyse the electronic structure for configurations relevant to molecular dissociation and adsorption of atomic hydrogen on a graphene single layer. An absolute band gap of 0.5 eV is found for the equilibrium optimum configuration for a narrow range of coverages ($θ\approx 0.25$). This value is in good agreement with experiment [Elias et al., Science {\bf 323}, 610 (2009)].

cond-mat.mtrl-sci↗

arXiv2010

Trapping of electrons near chemisorbed hydrogen on graphene

Chemical adsorption of atomic hydrogen on a negatively charged single layer graphene sheet has been analyzed with ab-initio Density Functional Theory calculations. We have simulated both finite clusters and infinite periodic systems to investigate the effect of different ingredients of the theory, e.g. exchange and correlation potentials, basis sets, etc. Hydrogen's electron affinity dominates the energetic balance in the charged systems and the extra electron is predominantly attracted to a region nearby the chemisorbed atom. The main consequences are: (i) the cancellation of the unpaired spin resulting in a singlet ground-state, and (ii) a stronger interaction between hydrogen and the graphene sheet.

cond-mat.mtrl-sci↗

arXiv2009

Ab-initio calculation of the effect of stress on the chemical activity of graphene

Graphene layers are stable, hard, and relatively inert. We study how tensile stress affects $σ$ and $π$ bonds and the resulting change in the chemical activity. Stress affects more strongly $π$ bonds that can become chemically active and bind to adsorbed species more strongly. Upon stretch, single C bonds are activated in a geometry mixing $120^{o}$ and $90^{o}$; an intermediate state between $sp^{2}$ and $sp^{3}$ bonding. We use ab-initio density functional theory to study the adsorption of hydrogen on large clusters and 2D periodic models for graphene. The influence of the exchange-correlation functional on the adsorption energy is discussed.

cond-mat.mtrl-sci↗

arXiv2009

Magnetic molecules created by hydrogenation of Polycyclic Aromatic Hydrocarbons

Present routes to produce magnetic organic-based materials adopt a common strategy: the use of magnetic species (atoms, polyradicals, etc.) as building blocks. We explore an alternative approach which consists of selective hydrogenation of Polycyclic Aromatic Hydrocarbons. Self-Consistent-Field (SCF) (Hartree-Fock and DFT) and multi-configurational (CISD and MCSCF) calculations on coronene and corannulene, both hexa-hydrogenated, show that the formation of stable high spin species is possible. The spin of the ground states is discussed in terms of the Hund rule and Lieb's theorem for bipartite lattices (alternant hydrocarbons in this case). This proposal opens a new door to magnetism in the organic world.

physics.atm-clus↗

arXiv2008

Transport regimes in surface disordered graphene sheets

We investigate the size scaling of the conductance of surface disordered graphene sheets of width W and length L. Metallic leads are attached to the sample ends across its width. At E ~ 0, the conductance scales with the system size as follows: i) For constant W/L, it remains constant as size is increased, at a value which depends almost lineally on that ratio; this scaling allows the definition of a conductivity value that results similar to the experimental one. ii) For fixed width, the conductance decreases exponentially with length L, both for ordered and disordered samples. Disorder reduces the exponential decay, leading to a higher conductance. iii) For constant length, conductance increases linearly with width W, a result that is exclusively due to the tails of the states of the metallic wide contact. iv) The average conductance does not show an appreciable dependence on magnetic field. Away from E = 0, the conductance shows the behavior expected in two-dimensional systems with surface disorder, i.e., ballistic transport.

cond-mat.mes-hall↗

arXiv2007

Strong covalent bonding between two graphene layers

We show that two graphene layers stacked directly on top of each other (AA stacking) form strong chemical bonds when the distance between planes is 0.156 nm. Simultaneously, C-C in-plane bonds are considerably weakened from partial double-bond (0.141 nm) to single bond (0.154 nm). This polymorphic form of graphene bilayer is meta-stable w.r.t. the one bound by van der Waals forces at a larger separation (0.335 nm) with an activation energy of 0.16 eV/cell. Similarly to the structure found in hexaprismane, C forms four single bonds in a geometry mixing 90^{0} and 120^{0} angles. Intermediate separations between layers can be stabilized under external anisotropic stresses showing a rich electronic structure changing from semimetal at van der Waals distance, to metal when compressed, to wide gap semiconductor at the meta-stable minimum.

cond-mat.mtrl-sci↗

arXiv2005

Confinement of hydrodynamic modes on a free surface and their quantum analogs

A subtle procedure to confine hydrodynamic modes on the free surface of a fluid is presented here. The experiment consists of a square vessel with an immersed square central well vibrating vertically so that the surface waves generated by the meniscus at the vessel boundary interfere with the bound states of the well. This is a classical analogy of a quantum well where some fundamental phenomena, such as bonding of states and interference between free waves and bound states, can be visualized and controlled. The above mentioned interference leads to a novel hydrodynamic transition from quasiperiodic to periodic patterns. Tight binding numerical calculations are performed here to show that our results could be transferred to design quantum confinements exhibiting electronic quasiperiodic surface states and their rational approximants for the first time.

physics.flu-dyn↗

arXiv2004

The one-particle Green's function of one.dimensional insulating materials

The single particle spectral-weight function (SWF) of the ionic Hubbard model at half filling is calculated in the cluster perturbation theory approximation. An abrupt change of regime in the low-energy region, near the chemical potential, is found at a critical value, $U_{c}$, of the coupling constant (Hubbard $U$). The SWF at the Fermi points $k_{F}$=$\pmπ/2$ jumps, as $U$ increases, from a two-peak structure, the gap edges, to a four-peak structure accompanied by a (non-vanishing) minimum of the charge-gap. The two inner peaks of this structure show very small dispersion (flat bands) away from the Fermi points, whereas the outer peaks mark the edges of the Hubbard bands. No other signatures of abrupt change are detected in the SWF. The two regimes are physically realized in the angle-resolved photoelectron spectra of $(TaSe_{4})_{2}I$, and the blue-bronze $K_{0.3}MoO_{3}$, respectively.

cond-mat.str-el↗

arXiv2004

Topology induced Kondo effect in hydrogenated Pt nanocontacts

It is shown that recent experimental data on electronic transport through Pt nanocontacts in the presence of hydrogen admit an explanation in terms of topological and electron-electron correlation grounds. A model Hamiltonian, which incorporates two orbitals on Pt atoms, a single orbital on hydrogens, and the on-site Coulomb repulsion on the H atoms, is solved exactly, and connected to Pt leads described by a Bethe lattice. When two weakly coupled H atoms are placed between the Pt electrodes transversally to the transport direction (as recently suggested) a Kondo effect related to the symmetry of the Pt-H couplings, stabilizes the conductance around one quantum with a single channel contributing to the current, in agreement with the experiments.

cond-mat.str-el↗

arXiv2003

Transport through an interacting system connected to leads

Keldysh formalism is used to get the current-voltage characteristic of a small system of interacting electrons described by a Hubbard model coupled to metallic wires. The numerical procedure is checked recovering well-known results for an Anderson impurity. When larger interacting regions are considered quite different results are obtained depending on whether the Hubbard part is half-filled or not. At half-filling the existence of a gap charge manifests itself making current exponentially small as a function both of the number of interacting sites and the value of U. The behavior changes at large voltages above the gap energy when activated charge transport takes place. On the contrary, for filling factors other than half, current goes through the interacting system suffering just a small amount of scattering at both connections. Conductance depends slightly on U and much more on the filling factor but not on the length of the interacting region.

cond-mat.str-el↗

arXiv2003

Electronic transport and vibrational modes in the smallest molecular bridge: H2 in Pt nanocontacts

We present a state-of-the-art first-principles analysis of electronic transport in a Pt nanocontact in the presence of H2 which has been recently reported by Smit et al. in Nature 419, 906 (2002). Our results indicate that at the last stages of the breaking of the Pt nanocontact two basic forms of bridge involving H can appear. Our claim is, in contrast to Smit et al.'s, that the main conductance histogram peak at G approx 2e^2/h is not due to molecular H2, but to a complex Pt2H2 where the H2 molecule dissociates. A first-principles vibrational analysis that compares favorably with the experimental one also supports our claim .

cond-mat.mtrl-sci↗

arXiv2003

Classical trajectories in quantum transport at the band center of bipartite lattices with or without vacancies

Here we report on several anomalies in quantum transport at the band center of a bipartite lattice with vacancies that are surely due to its chiral symmetry, namely: no weak localization effect shows up, and, when leads have a single channel the transmission is either one or zero. We propose that these are a consequence of both the chiral symmetry and the large number of states at the band center. The probability amplitude associated to the eigenstate that gives unit transmission ressembles a classical trajectory both with or without vacancies. The large number of states allows to build up trajectories that elude the blocking vacancies explaining the absence of weak localization.

cond-mat.mes-hall↗

arXiv2003

Molecular electronics and first-principles methods

We discuss the key steps that have to be followed to calculate coherent quantum transport in molecular and atomic-scale systems, making emphasis on the ab-initio Gaussian Embedded Cluster Method recently developed by the authors. We present various results on a simple system such as a clean Au nanocontact and the same nanocontact in the presence of hydrogen that illustrate the applicability of this method in the study and interpretation of a large range of experiments in the field of molecular electronics.

cond-mat.mtrl-sci↗