142 research outputs found
Renormalization of Optical Excitations in Molecules near a Metal Surface
The lowest electronic excitations of benzene and a set of donor-acceptor
molecular complexes are calculated for the gas phase and on the Al(111) surface
using the many-body Bethe-Salpeter equation (BSE). The energy of the
charge-transfer excitations obtained for the gas phase complexes are found to
be around 10% lower than the experimental values. When the molecules are placed
outside the surface, the enhanced screening from the metal reduces the exciton
binding energies by several eVs and the transition energies by up to 1 eV
depending on the size of the transition-generated dipole. As a striking
consequence we find that close to the metal surface the optical gap of benzene
can exceed its quasiparticle gap. A classical image charge model for the
screened Coulomb interaction can account for all these effects which, on the
other hand, are completely missed by standard time-dependent density functional
theory.Comment: 4 pages, 3 figures; revised versio
Graphene on metals: a Van der Waals density functional study
We use density functional theory (DFT) with a recently developed van der
Waals density functional (vdW-DF) to study the adsorption of graphene on Al,
Cu, Ag, Au, Pt, Pd, Co and Ni(111) surfaces. In constrast to the local density
approximation (LDA) which predicts relatively strong binding for Ni,Co and Pd,
the vdW-DF predicts weak binding for all metals and metal-graphene distances in
the range 3.40-3.72 \AA. At these distances the graphene bandstructure as
calculated with DFT and the many-body GW method is basically unaffected
by the substrate, in particular there is no opening of a band gap at the
-point.Comment: 4 pages, 3 figure
Inversed linear dichroism in F <em>K</em>-edge NEXAFS spectra of fluorinated planar aromatic molecules
et al.The symmetry and energy distribution of unoccupied molecular orbitals is addressed in this work by means of NEXAFS and density functional theory calculations for planar, fluorinated organic semiconductors (perfluorinated copper phthalocyanines and perfluoropentacene). We demonstrate how molecular orbitals with significant density of states on the fluorine atoms show different symmetry from those mainly located on C and N atoms. As a result, the angle-dependent linear dichroism in NEXAFS F K-edge spectra is inversed with respect to that in the C and N K-edges. In addition, the significant overlap in energy of π * and σ * orbitals throughout the F K-edge spectrum hampers its use for analysis of molecular orientations from angle-dependent NEXAFS measurements. © 2012 American Physical Society.J.E.O. and A.R. acknowledge funding from the Spanish MEC through Grants No. FIS2011-65702-C02-01, No. MAT2010-21156-C03-01, and No. PIB2010US-00652, and from the Basque Government through Grants No. IT-257-07 and No. IT-319-07. A.R. additionally acknowledges that financial support was provided by ACI-Promociona Grant No. ACI2009-1036 and the European Research Council Advanced Grant DYNamo (ERC-2010-AdG, Proposal No. 267374). A.S. acknowledges the support of the Research Funds of the University of Helsinki and the Academy of Finland through Contract No. 1127462, Centers of Excellence Program, and the National Graduate School in Materials Physics. J.M.G.L. acknowledges support from The Lundbeck Foundation’s Center for Atomic-Scale Materials Design and the Danish Center for Scientific Computing.Peer Reviewe
Quasiparticle interfacial level alignment of highly hybridized frontier levels: HO on TiO(110)
Knowledge of the frontier levels' alignment prior to photo-irradiation is
necessary to achieve a complete quantitative description of HO
photocatalysis on TiO(110). Although HO on rutile TiO(110) has been
thoroughly studied both experimentally and theoretically, a quantitative value
for the energy of the highest HO occupied levels is still lacking. For
experiment, this is due to the HO levels being obscured by hybridization
with TiO(110) levels in the difference spectra obtained via ultraviolet
photoemission spectroscopy (UPS). For theory, this is due to inherent
difficulties in properly describing many-body effects at the
HO-TiO(110) interface. Using the projected density of states (DOS) from
state-of-the-art quasiparticle (QP) , we disentangle the adsorbate and
surface contributions to the complex UPS spectra of HO on TiO(110). We
perform this separation as a function of HO coverage and dissociation on
stoichiometric and reduced surfaces. Due to hybridization with the TiO(110)
surface, the HO 3a and 1b levels are broadened into several peaks
between 5 and 1 eV below the TiO(110) valence band maximum (VBM). These
peaks have both intermolecular and interfacial bonding and antibonding
character. We find the highest occupied levels of HO adsorbed intact and
dissociated on stoichiometric TiO(110) are 1.1 and 0.9 eV below the VBM. We
also find a similar energy of 1.1 eV for the highest occupied levels of HO
when adsorbed dissociatively on a bridging O vacancy of the reduced surface. In
both cases, these energies are significantly higher (by 0.6 to 2.6 eV) than
those estimated from UPS difference spectra, which are inconclusive in this
energy region. Finally, we apply self-consistent QP (scQP1) to obtain
the ionization potential of the HO-TiO(110) interface.Comment: 12 pages, 12 figures, 1 tabl
Effect of Layer-Stacking on the Electronic Structure of Graphene Nanoribbons
The evolution of electronic structure of graphene nanoribbons (GNRs) as a
function of the number of layers stacked together is investigated using
\textit{ab initio} density functional theory (DFT) including interlayer van der
Waals interactions. Multilayer armchair GNRs (AGNRs), similar to single-layer
AGNRs, exhibit three classes of band gaps depending on their width. In zigzag
GNRs (ZGNRs), the geometry relaxation resulting from interlayer interactions
plays a crucial role in determining the magnetic polarization and the band
structure. The antiferromagnetic (AF) interlayer coupling is more stable
compared to the ferromagnetic (FM) interlayer coupling. ZGNRs with the AF
in-layer and AF interlayer coupling have a finite band gap while ZGNRs with the
FM in-layer and AF interlayer coupling do not have a band gap. The ground state
of the bi-layer ZGNR is non-magnetic with a small but finite band gap. The
magnetic ordering is less stable in multilayer ZGNRs compared to single-layer
ZGNRs. The quasipartcle GW corrections are smaller for bilayer GNRs compared to
single-layer GNRs because of the reduced Coulomb effects in bilayer GNRs
compared to single-layer GNRs.Comment: 10 pages, 5 figure
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