Eduardo Costa Girão

Functionalization of single-wall carbon nanotubes through chloroform adsorption: theory and experiment

The interaction of chloroform (CHCl(3)) with single-wall carbon nanotubes (SWCNT) is investigated using both first principles calculations based on Density Functional Theory and vibrational spectroscopy experiments. CHCl(3) adsorption on pristine, defective, and carboxylated SWCNTs is simulated, thereby gaining a good understanding of the adsorption process of this molecule on SWCNT surfaces. The results predict a physisorption regime in all cases. These calculations point out that SWCNTs are promising materials for extracting trihalomethanes from the environment. Theoretical predictions on the stability of the systems SWCNT-CCl(2) and SWCNT-COCCl(3) are confirmed by experimental TGA data and Fourier Transform Infrared Spectroscopy (FT-IR) experiments. Results from resonance Raman scattering experiments indicate that electrons are transferred from the SWCNTs to the attached groups and these results are in agreement with the predictions made by ab initio calculations.

Improved All-Carbon Spintronic Device Design

The discovery of magnetism in carbon structures containing zigzag edges has stimulated new directions in the development and design of spintronic devices. However, many of the proposed structures are designed without incorporating a key phenomenon known as topological frustration, which leads to localized non-bonding states (free radicals), increasing chemical reactivity and instability. By applying graph theory, we demonstrate that topological frustrations can be avoided while simultaneously preserving spin ordering, thus providing alternative spintronic designs. Using tight-binding calculations, we show that all original functionality is not only maintained but also enhanced, resulting in the theoretically highest performing devices in the literature today. Furthermore, it is shown that eliminating armchair regions between zigzag edges significantly improves spintronic properties such as magnetic coupling.

Nicotine adsorption on single wall carbon nanotubes.

This work reports a theoretical study of nicotine molecules interacting with single wall carbon nanotubes (SWCNTs) through ab initio calculations within the framework of density functional theory (DFT). Different adsorption sites for nicotine on the surface of pristine and defective (8,0) SWCNTs were analyzed and the total energy curves, as a function of molecular position relative to the SWCNT surface, were evaluated. The nicotine adsorption process is found to be energetically favorable and the molecule-nanotube interaction is intermediated by the tri-coordinated nitrogen atom from the nicotine. It is also predicted the possibility of a chemical bonding between nicotine and SWCNT through the di-coordinated nitrogen.

Electronic transport properties of assembled carbon nanoribbons.

Graphitic nanowiggles (GNWs) are 1D systems with segmented graphitic nanoribbon GNR edges of varying chiralities. They are characterized by the presence of a number of possible different spin distributions along their edges and by electronic band-gaps that are highly sensitive to the details of their geometry. These two properties promote these experimentally observed carbon nanostructures as some of the most promising candidates for developing high-performance nanodevices. Here, we highlight this potential with a detailed understanding of the electronic processes leading to their unique spin-state dependent electronic quantum transport properties. The three classes of GNWs containing at least one zigzag edge (necessary to the observation of multiple-magnetic states) are considered in two distinct geometries: a perfectly periodic system and in a one-GNW-cell system sandwiched between two semi-infinite terminals made up of straight GNRs. The present calculations establish a number of elementary rules to relate fundamental electronic transport functionality, electronic energy, the system geometry, and spin state.

Quantum Dots in Graphene Nanoribbons

Graphene quantum dots (GQDs) hold great promise for applications in electronics, optoelectronics, and bioelectronics, but the fabrication of widely tunable GQDs has remained elusive. Here, we report the fabrication of atomically precise GQDs consisting of low-bandgap N = 14 armchair graphene nanoribbon (AGNR) segments that are achieved through edge fusion of N = 7 AGNRs. The so-formed intraribbon GQDs reveal deterministically defined, atomically sharp interfaces between wide and narrow AGNR segments and host a pair of low-lying interface states. Scanning tunneling microscopy/spectroscopy measurements complemented by extensive simulations reveal that their energy splitting depends exponentially on the length of the central narrow bandgap segment. This allows tuning of the fundamental gap of the GQDs over 1 order of magnitude within a few nanometers length range. These results are expected to pave the way for the development of widely tunable intraribbon GQD-based devices.

A single molecule rectifier with strong push-pull coupling

We theoretically investigate the electronic charge transport in a molecular system composed of a donor group (dinitrobenzene) coupled to an acceptor group (dihydrophenazine) via a polyenic chain (unsaturated carbon bridge). Ab initio calculations based on the Hartree-Fock approximations are performed to investigate the distribution of electron states over the molecule in the presence of an external electric field. For small bridge lengths (n=0-3) we find a homogeneous distribution of the frontier molecular orbitals, while for n>3 a strong localization of the lowest unoccupied molecular orbital is found. The localized orbitals in between the donor and acceptor groups act as conduction channels when an external electric field is applied. We also calculate the rectification behavior of this system by evaluating the charge accumulated in the donor and acceptor groups as a function of the external electric field. Finally, we propose a phenomenological model based on nonequilibrium Greens function to rationalize the ab initio findings.

Electronic transport in three-terminal triangular carbon nanopatches

The electronic transport properties of three-terminal graphene-based triangular patches are investigated using a combination of semi-empirical tight-binding calculations and Greens function-based transport theory within Landauers framework. The junctions are composed of a triangular structure based on armchair edged graphene nanoribbons. We show how details of the central region influence the resonant electronic transport across the triangular patches and highlight the unique features of the current flow as a function of geometry. These properties indicate an array of functionalities for the development of carbon-based complex nanocircuits and operational devices at the nanoscale.

Electronic transmission selectivity in multiterminal graphitic nanorings

Graphene based toroidal carbon nanostructures possess unique electronic properties induced by quantum confinement and cyclic boundary conditions imposed to the wave-functions along the circumference. We used a tight-binding approach to demonstrate that nanoribbon and nanotube based ring structures have energy-dependent selection rules for electron transmission, especially when they are connected to a large number of terminals.

Tuning the electronic and quantum transport properties of nitrogenated holey graphene nanoribbons

Recently, a new semiconductor two-dimensional (2D) material, namely, holey nitrogenated graphene 2D crystal (C2N-h2D), has been fabricated by using a bottom-up wet-chemical reaction. Using first-principles density functional theory (DFT) combined with the non-equilibrium Greens function (NEGF) technique, we investigate the atomic, electronic and quantum transport properties of porous C2N nanoribbons having both zigzag- and armchair-terminated edges. The zigzag C2N-h nanoribbons (ZC2N-hNRs) are semiconductors with an indirect band gap that decreases as the ribbon width increases. Meanwhile, the armchair C2N-h nanoribbons (AC2N-hNRs) show a metallic behavior for all ribbon widths, except for one of the candidates considered in this study, which presents a small band gap (0.14 eV). Interestingly, non-equilibrium calculations suggest that these structures display edge-dependent electronic transport properties where the armchair C2N-hNRs show a strong negative differential resistance (NDR) behavior with current peak-to-valley ratios that remarkably increase with increasing ribbon width, and non-linear current–voltage characteristics were found for the zigzag C2N-hNRs.

Modeling and simulation of electron transport at the nanoscale: illustrations in low-dimensional carbon nanostructures

This chapter showcases selected illustrations of various manifestations of nanoscale and molecular electronic effects as investigated by quantum mechanical methods. The examples include results demonstrating (1) how graphitic nanoribbons can be assembled into multiterminal networks and the influence on electron transport; (2) how the position of a single embedded molecule can be modified to change the overall conduction state of a nanowire; (3) how carbon nanotubes can be assembled into complex covalent arrays and how these can be obtained experimentally; (4) how quantum interference can be understood as emerging from the presence of multiple levels of confinements in carbon nanorings; (5) how new functionality emerges at the nanoscale due to the interplay of magnetic, electronic, and structural properties of individual graphitic nanoribbons assembled into wiggle-like structures; and (6) how quantum chemical modeling can lead to the design of electrodes with enhanced interfaces for molecular coupling.