A critical analysis of vacancy-induced magnetism in mono and bilayer graphene

The observation of intrinsic magnetic order in graphene and graphene-based materials relies on the formation of magnetic moments and a sufficiently strong mutual interaction. Vacancies are arguably considered the primary source of magnetic moments. Here we present an in-depth density functional theory study of the spin-resolved electronic structure of (monoatomic) vacancies in graphene and bilayer graphene. We use two different methodologies: supercell calculations with the SIESTA code and cluster-embedded calculations with the ALACANT package. Our results are conclusive: The vacancy-induced extended $\pi$ magnetic moments, which present long-range interactions and are capable of magnetic ordering, vanish at any experimentally relevant vacancy concentration. This holds for $\sigma$-bond passivated and un-passivated reconstructed vacancies, although, for the un-passivated ones, the disappearance of the $\pi$ magnetic moments is accompanied by a very large magnetic susceptibility. Only for the unlikely case of a full $\sigma$-bond passivation, preventing the reconstruction of the vacancy, a full value of 1$\mu_B$ for the $\pi$ extended magnetic moment is recovered for both mono and bilayer cases. Our results put on hold claims of vacancy-induced ferromagnetic or antiferromagnetic order in graphene-based systems, while still leaving the door open to $\sigma$-type paramagnetism.Comment: Submitted to Phys. Rev B, 9 page

Graphene/Li-Ion battery

Density function theory calculations were carried out to clarify storage states of Lithium (Li) ions in graphene clusters. The adsorption energy, spin polarization, charge distribution, electronic gap, surface curvature and dipole momentum were calculated for each cluster. Li-ion adsorbed graphene, doped by one Li atom is spin polarized, so there would be different gaps for different spin polarization in electrons. Calculation results demonstrated that a smaller cluster between each two larger clusters is preferable, because it could improve graphene Li-ion batteries; consequently, the most proper graphene anode structure has been proposed.Comment: 19 pages, 7 figures, 1 tabl

Superhalogen and Superacid

A superhalogen $\rm{F@C_{20}(CN)_{20}}$ and a corresponding Br{\o}nsted superacid were designed and investigated on DFT and DLPNO-CCSD(T) levels of theory. Calculated compounds have outstanding electron affinity and deprotonation energy, respectively. We consider superacid $\rm{H[F@C_{20}(CN)_{20}]}$ to be able to protonate molecular nitrogen. The stability of these structures is discussed, while some of the previous predictions concerning Br{\o}nsted superacids of record strength are doubted.Comment: 11 pages (main paper), 32 pages (supporting information), 10 figures, 10 tables, 62 reference

Nonlocal pseudopotentials and magnetic fields

We show how to describe the coupling of electrons to non-uniform magnetic fields in the framework of the widely used norm-conserving pseudopotential appro ximation for electronic structure calculations. Our derivation applies to magnetic fields that are smooth on the scale of the core region. The method is validated by application to the calculation of the magnetic susceptibility of molecules. Our results are compared with high quality all electron quantum chemical results, and another recently proposed formalism.Comment: 4 pages, submitted to Physical Review Letter

Identification of the Atomic Scale Structures of the Gold-Thiol Interfaces of Molecular Nanowires by Inelastic Tunneling Spectroscopy

We examine theoretically the effects of the bonding geometries at the gold-thiol interfaces on the inelastic tunneling spectra of propanedithiolate (PDT) molecules bridging gold electrodes and show that inelastic tunneling spectroscopy combined with theory can be used to determine these bonding geometries experimentally. With the help of density functional theory, we calculate the relaxed geometries and vibrational modes of extended molecules each consisting of one or two PDT molecules connecting two gold nanoclusters. We formulate a perturbative theory of inelastic tunneling through molecules bridging metal contacts in terms of elastic transmission amplitudes, and use this theory to calculate the inelastic tunneling spectra of the gold-PDT-gold extended molecules. We consider PDT molecules with both trans and gauche conformations bound to the gold clusters at top, bridge and hollow bonding sites. Comparing our results with the experimental data of Hihath et al. [Nano Lett. 8, 1673 (2008)], we identify the most frequently realized conformation in the experiment as that of trans molecules top-site bonded to both electrodes. We find the switching from the 42 meV vibrational mode to the 46 meV mode observed in the experiment to be due to the transition of trans molecules from mixed top-bridge to pure top-site bonding geometries. Our results also indicate that gauche molecular conformations and hollow site bonding did not contribute significantly to the experimental inelastic tunneling spectra. For pairs of PDT molecules connecting the gold electrodes in parallel we find total elastic conductances close to twice those of single molecules bridging the contacts with similar bonding conformations and small splittings of the vibrational mode energies for the modes that are the most sensitive to the molecule-electrode bonding geometries.Comment: 14 pages, 8 figures, 1 table. arXiv admin note: significant text overlap with arXiv:1103.2378; http://jcp.aip.org/resource/1/jcpsa6/v136/i1/p014703_s

Unusual conductance of polyyne-based molecular wires

We report a full self-consistent ab initio calculation of the current-voltage curve and the conductance of thiolate capped polyynes in contact with gold electrodes. We find the conductance of polyynes an order of magnitude larger compared with other conjugated oligomers. The reason lies in the position of the Fermi level deep in the HOMO related resonance. With the conductance weakly dependent on the applied bias and almost independent of the length of the molecular chain, polyynes appear as nearly perfect molecular wires.Comment: 4 pages, 5 figures, 3 table

Electromagnetic Vacuum of Complex Media: Dipole Emission vs. Light Propagation, Vacuum Energy, and Local Field Factors

We offer a unified approach to several phenomena related to the electromagnetic vacuum of a complex medium made of point electric dipoles. To this aim, we apply the linear response theory to the computation of the polarization field propagator and study the spectrum of vacuum fluctuations. The physical distinction among the local density of states which enter the spectra of light propagation, total dipole emission, coherent emission, total vacuum energy and Schwinger-bulk energy is made clear. Analytical expressions for the spectrum of dipole emission and for the vacuum energy are derived. Their respective relations with the spectrum of external light and with the Schwinger-bulk energy are found. The light spectrum and the Schwinger-bulk energy are determined by the Dyson propagator. The emission spectrum and the total vacuum energy are determined by the polarization propagator. An exact relationship of proportionality between both propagators is found in terms of local field factors. A study of the nature of stimulated emission from a single dipole is carried out. Regarding coherent emission, it contains two components. A direct one which is transferred radiatively and directly from the emitter into the medium and whose spectrum is that of external light. And an indirect one which is radiated by induced dipoles. The induction is mediated by one (and only one) local field factor. Regarding the vacuum energy, we find that in addition to the Schwinger-bulk energy the vacuum energy of an effective medium contains local field contributions proportional to the resonant frequency and to the spectral line-width.Comment: Typos fixed, journal ref. adde

Photoassociation of a cold atom-molecule pair: long-range quadrupole-quadrupole interactions

The general formalism of the multipolar expansion of electrostatic interactions is applied to the calculation the potential energy between an excited atom (without fine structure) and a ground state diatomic molecule at large separations. Both partners exhibit a permanent quadrupole moment, so that their mutual quadrupole-quadrupole long-range interaction is attractive enough to bind trimers. Numerical results are given for an excited Cs(6P) atom and a ground state Cs2 molecule. The prospects for achieving photoassociation of a cold atom/dimer pair is thus discussed and found promising. The formalism can be easily generalized to the long-range interaction between molecules to investigate the formation of cold tetramers.Comment: 5 figure

Adsorption of arsenate on Fe-(hydr)oxide

Adsorption using metal oxide materials has been demonstrated to be an effective technique to remove hazardous materials from water, due to its easy operation, low cost, and high efficiency. The high number of oxyanions in aquatic ecosystems causes serious pollution problems. Removal of arsenate (H2AsO4 -), is one of the major concerns, since it is a highly toxic anion for life. Within the metal oxides, the iron oxide is considered as a suitable material for the elimination of oxyanions. The adsorption of H2AsO4 - on Fe-(hydr)oxide is through the formation of inner or outer sphere complexes. In this work, through computational methods, a complete characterization of the adsorbed surface complexes was performed. Three different pH conditions were simulated (acidic, intermediate and basic), and it was found that, the thermodynamic favourability of the different adsorbed complexes was directly related to the pH. Monodentate complex (MM1) was the most thermodynamically favourable complex with an adsorption energy of -96.0kJ/mol under intermediate pH conditions. © Published under licence by IOP Publishing Ltd