20,189 research outputs found
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
magnetic moments, which present long-range interactions and are capable of
magnetic ordering, vanish at any experimentally relevant vacancy concentration.
This holds for -bond passivated and un-passivated reconstructed
vacancies, although, for the un-passivated ones, the disappearance of the
magnetic moments is accompanied by a very large magnetic susceptibility. Only
for the unlikely case of a full -bond passivation, preventing the
reconstruction of the vacancy, a full value of 1 for the 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 -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 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
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
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