Graphene catalyzes the reversible formation of a C-C bond between two molecules.

Carbon deposits are well-known inhibitors of transition metal catalysts. In contrast to this undesirable behavior, here we show that epitaxial graphene grown on Ru(0001) promotes the reversible formation of a C-C bond between -CH2CN and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ). The catalytic role of graphene is multifaceted: First, it allows for an efficient charge transfer between the surface and the reactants, thus favoring changes in carbon hybridization; second, it holds the reactants in place and makes them reactive. The reaction is fully reversible by injecting electrons with an STM tip on the empty molecular orbitals of the product. The making and breaking of the C-C bond is accompanied by the switching off and on of a Kondo resonance, so that the system can be viewed as a reversible magnetic switch controlled by a chemical reaction.

Plasmon Modes of Graphene Nanoribbons with Periodic Planar Arrangements.

Among their amazing properties, graphene and related low-dimensional materials show quantized charge-density fluctuations-known as plasmons-when exposed to photons or electrons of suitable energies. Graphene nanoribbons offer an enhanced tunability of these resonant modes, due to their geometrically controllable band gaps. The formidable effort made over recent years in developing graphene-based technologies is however weakened by a lack of predictive modeling approaches that draw upon available ab initio methods. An example of such a framework is presented here, focusing on narrow-width graphene nanoribbons, organized in periodic planar arrays. Time-dependent density-functional calculations reveal unprecedented plasmon modes of different nature at visible to infrared energies. Specifically, semimetallic (zigzag) nanoribbons display an intraband plasmon following the energy-momentum dispersion of a two-dimensional electron gas. Semiconducting (armchair) nanoribbons are instead characterized by two distinct intraband and interband plasmons, whose fascinating interplay is extremely responsive to either injection of charge carriers or increase in electronic temperature. These oscillations share some common trends with recent nanoinfrared imaging of confined edge and surface plasmon modes detected in graphene nanoribbons of 100-500 nm width.

Core-hole effects in fullerene molecules and small-diameter conducting nanotubes: a density functional theory study.

Core-hole induced electron excitations in fullerene molecules, and small-diameter conducting carbon nanotubes, are studied using density functional theory with minimal, split-valence, and triply-split-valence basis sets plus the generalized gradient approximation by Perdew-Burke-Ernzerhof for exchange and correlation. Finite-size computations are performed on the carbon atoms of a C(60) Bucky ball and a piece of (3, 3) armchair cylindrical network, terminated by hydrogen atoms, while periodically boundary conditions are imposed on a (3, 3) nanotube unit cell. Sudden creation of the core state is simulated by replacing a 1s electron pair, localized at a central site of the structures, with the effective pseudo-potentials of both neutral and ionized atomic carbon. Excited states are obtained from the ground-state (occupied and empty) electronic structure of the ionized systems, and their overlaps with the ground state of the neutral systems are computed. These overlaps enter Fermi's golden rule, which is corrected with lifetime and finite-temperature effects to simulate the many-electron response of the nanoobjects. A model based on the linked cluster expansion of the vacuum persistence amplitude of the neutral systems, in a parametric core-hole perturbation, is developed and found to be reasonably consistent with the density functional theory method. The simulated spectrum of the fullerene molecule is found to be in good agreement with x-ray photoemission experiments on thick C(60) films, reproducing the low energy satellites at excitation energies below 4 eV within a peak position error of ca. 0.3 eV. The nanotube spectra show some common features within the same experiments and describe well the measured x-ray photoelectron lineshape from nanotube bundles with an average diameter of 1.2 nm.

Role of many body shake-up in core-valence-valence electron emission from single wall carbon nanotubes.

Auger core-valence-valence transitions from single wall Carbon nanotubes are studied using a tight-binding calculational scheme with nearest neighbor overlap, hopping interactions, and a double-zeta basis set. The resulting Hamiltonian approximates the unperturbed pi and sigma bands of the nanomaterials coupled with the free electron states outside the solid and the core-hole. As a first step, the Fermi's golden rule is applied to determine the so called one-electron spectrum of emitted electrons from different tubes, in which either the neutralizing or the ejected electrons, in the initial state, lie within nearest neighboring atomic sites to the core-hole. Many-body corrections are effectively modeled using a broadening function, which accounts for dynamic screening effects involving the initial and final states. Particular attention is paid to the asymmetric component of the broadening function, responsible for the shake-up of pi electrons. Finally, the Cini-Sawatzky distortion function is used to describe the final state effect of the hole-hole interaction. A quantitative estimation of the interplay of shake-up processes is proposed by adjusting the asymmetric parameters of the broadening function to reproduce measurements of Auger electrons ejected from bundles of single wall Carbon nanotubes.

Secondary electron spectra of graphene on Ni(111) surface.

We report on kinetic energy distributions of electrons emitted during bombardment of graphene adsorbed on a Ni(111) surface by 0.5-0.9 keV electrons. The spectra reveal several peaks superimposed on the background of cascade electrons. The position of these peaks does not depend significantly on primary electron energy but show a remarkable angular dependence, indicating that they are directly related to the empty bands above the vacuum level of the sample.

Charge transfer in single and multiple scattering events at metal surfaces: a wavepacket study of the Na(+)/Cu(100) system.

Resonant neutralization of hyperthermal energy Na(+) ions impinging on Cu(100) surfaces is studied, focusing on two specific collision events: one in which the projectile is reflected off the surface, the other in which the incident atom penetrates the outer surface layers initiating a series of scattering processes, within the target, and coming out together with a single surface atom. A semi-empirical model potential is adopted that embeds: (i) the electronic structure of the sample, (ii) the central field of the projectile, and (iii) the contribution of the Cu atom ejected in multiple scattering events. The evolution of the ionization orbital of the scattered atom is simulated, backwards in time, using a wavepacket propagation algorithm. The output of the approach is the neutralization probability, obtained by projecting the time-reversed valence wavefunction of the projectile onto the initially filled conduction band states. The results are in agreement with available data from the literature (Keller et al 1995 Phys. Rev. Lett. 75 1654) indicating that the motion of surface atoms, exiting the targets with kinetic energies of the order of a few electronvolts, plays a significant role in the final charge state of projectiles.

Secondary electron emission spectra from clean and cesiated Al surfaces: the role of plasmon decay and data analysis for applications.

We report measurements of energy spectra of secondary electrons emitted from clean and cesiated aluminum surfaces under the impact of 130 eV electrons. Measurements show that the decay of bulk and surface plasmons dominates the electron emission. In contrast with theoretical calculations, our experiments indicate that the electron collision cascade inside the solid produced by electrons excited by plasmon decay do not contribute significantly to electron emission. A simple analysis of electron energy distributions measured as a function of Cs surface coverage allows separation of rediffused incident electrons from the continuum background of true secondary electrons. The result shows that yields of rediffused electrons used in several applications may have been significantly overestimated.