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Register a new userCharge transfer and weak bonding between molecular oxygen and graphene zigzag edges at low temperatures
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Electron paramagnetic resonance (EPR) study of air-physisorbed defective carbon nano-onions evidences in favor of microwave assisted formation of weakly-bound paramagnetic complexes comprising negatively-charged O2- ions and edge carbon atoms carrying pi-electronic spins. These complexes being located on the graphene edges are stable at low temperatures but irreversibly dissociate at temperatures above 50-60 K. These EPR findings are justified by density functional theory (DFT) calculations demonstrating transfer of an electron from the zigzag edge of graphene-like material to oxygen molecule physisorbed on the graphene sheet edge. This charge transfer causes changing the spin state of the adsorbed oxygen molecule from S = 1 to S = 1/2 one. DFT calculations show significant changes of adsorption energy of oxygen molecule and robustness of the charge transfer to variations of the graphene-like substrate morphology (flat and corrugated mono- and bi-layered graphene) as well as edges passivation. The presence of H- and COOH- terminated edge carbon sites with such corrugated substrate morphology allows formation of ZE-O2- paramagnetic complexes characterized by small (<50 meV) binding energies and also explains their irreversible dissociation as revealed by EPR.
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Here we study the electronic properties of cuprate/manganite interfaces. By means of atomic resolution electron microscopy and spectroscopy, we produce a subnanometer scale map of the transition metal oxidation state profile across the interface between the high $T_c$ superconductor YBa$_2$Cu$_3$O$_{7-delta}$ and the colossal magnetoresistance compound (La,Ca)MnO$_3$. A net transfer of electrons from manganite to cuprate with a peculiar non-monotonic charge profile is observed. Model calculations rationalize the profile in terms of the competition between standard charge transfer tendencies (due to band mismatch), strong chemical bonding effects across the interface, and Cu substitution into the Mn lattice, with different characteristic length scales.
Monatomic metal (e.g. silver) structures could form preferably at graphene edges. We explore their structural and electronic properties by performing density functional theory based first-principles calculations. The results show that cohesion between metal atoms, as well as electronic coupling between metal atoms and graphene edges offer remarkable structural stability of the hybrid. We find that the outstanding mechanical properties of graphene allow tunable properties of the metal monatomic structures by straining the structure. The concept is extended to metal rings and helices that form at open ends of carbon nanotubes and edges of twisted graphene ribbons. These findings demostrate the role of graphene edges as an efficient one-dimensional template for low-dimensional metal structures that are mechanotunable.
The cubic (c) and monoclinic (m) polymorphs of Gd2O3 were studied using the combined analysis of several materials science techniques - X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) spectroscopy. Density functional theory (DFT) based calculations for the samples under study were performed as well. The cubic phase of gadolinium oxide (c-Gd2O3) synthesized using a precipitation method exhibits spheroidal-like nanoclusters with well-defined edges assembled from primary nanoparticles with an average size of 50 nm, whereas the monoclinic phase of gadolinium oxide (m-Gd2O3) deposited using explosive pyrolysis has a denser structure compared with natural gadolinia. This phase also has a structure composed of three-dimensional complex agglomerates without clear-edged boundaries that are ~21 nm in size plus a cubic phase admixture of only 2 at. % composed of primary edge-boundary nanoparticles ~15 nm in size. These atomic features appear in the electronic structure as different defects ([Gd...O-OH] and [Gd...O-O]) and have dissimilar contributions to the charge-transfer processes among the appropriate electronic states with ambiguous contributions in the Gd 5p - O 2s core-like levels in the valence band structures. The origin of [Gd...O-OH] defects found by XPS was well-supported by PL analysis. The electronic and atomic structures of the synthesized gadolinias calculated using DFT were compared and discussed on the basis of the well-known joint OKT-van der Laan model, and good agreement was established.
Low-energy Landau levels of AB-stacked zigzag graphene ribbons in the presence of a uniform perpendicular magnetic field (textbf{B}) are investigated by the Peierls coupling tight-binding model. State energies and associated wave functions are dominated by the textbf{B}-field strength and the $k_z$-dependent interribbon interactions. The occupied valence bands are asymmetric to the unoccupied conduction bands about the Fermi level. Many doubly degenerate Landau levels and singlet curving magnetobands exist along $k_x$ and $k_z$ directions, respectively. Such features are directly reflected in density of states, which exhibits a lot of asymmetric prominent peaks because of 1D curving bands. The $k_z$-dependent interribbon interactions dramatically modify the magnetobands, such as the lift of double degeneracy, the change of state energies, and the production of two groups of curving magnetobands. They also change the characteristics of the wave functions and cause the redistribution of the charge carrier density. The $k_z$-dependent wave functions are further used to predict the selection rule of the optical transition.
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 ribbons stability. Thus, charging and its consequences should be investigated.Total energy calculations of finite ribbons using spin polarized Density Functional Theory (DFT) show that ribbons 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.
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