718 research outputs found
Imaging Pauli repulsion in scanning tunneling microscopy
A scanning tunneling microscope (STM) has been equipped with a nanoscale
force sensor and signal transducer composed of a single D2 molecule that is
confined in the STM junction. The uncalibrated sensor is used to obtain
ultra-high geometric image resolution of a complex organic molecule adsorbed on
a noble metal surface. By means of conductance-distance spectroscopy and
corresponding density functional calculations the mechanism of the
sensor/transducer is identified. It probes the short-range Pauli repulsion and
converts this signal into variations of the junction conductance.Comment: 4 pages, 4 figures, accepted to Phys. Rev. Let
Electrical transport through a mechanically gated molecular wire
A surface-adsorbed molecule is contacted with the tip of a scanning tunneling
microscope (STM) at a pre-defined atom. On tip retraction, the molecule is
peeled off the surface. During this experiment, a two-dimensional differential
conductance map is measured on the plane spanned by the bias voltage and the
tip-surface distance. The conductance map demonstrates that tip retraction
leads to mechanical gating of the molecular wire in the STM junction. The
experiments are compared with a detailed ab initio simulation. We find that
density functional theory (DFT) in the local density approximation (LDA)
describes the tip-molecule contact formation and the geometry of the molecular
junction throughout the peeling process with predictive power. However, a
DFT-LDA-based transport simulation following the non-equilibrium Green's
functions (NEGF) formalism fails to describe the behavior of the differential
conductance as found in experiment. Further analysis reveals that this failure
is due to the mean-field description of electron correlation in the local
density approximation. The results presented here are expected to be of general
validity and show that, for a wide range of common wire configurations,
simulations which go beyond the mean-field level are required to accurately
describe current conduction through molecules. Finally, the results of the
present study illustrate that well-controlled experiments and concurrent ab
initio transport simulations that systematically sample a large configuration
space of molecule-electrode couplings allow the unambiguous identification of
correlation signatures in experiment.Comment: 31 pages, 10 figure
Quasiparticle energies for large molecules: a tight-binding GW approach
We present a tight-binding based GW approach for the calculation of
quasiparticle energy levels in confined systems such as molecules. Key
quantities in the GW formalism like the microscopic dielectric function or the
screened Coulomb interaction are expressed in a minimal basis of spherically
averaged atomic orbitals. All necessary integrals are either precalculated or
approximated without resorting to empirical data. The method is validated
against first principles results for benzene and anthracene, where good
agreement is found for levels close to the frontier orbitals. Further, the size
dependence of the quasiparticle gap is studied for conformers of the polyacenes
() up to n = 30.Comment: 10 pages, 5 eps figures submitted to Phys. Rev.
Structural relaxations in electronically excited poly(para-phenylene)
Structural relaxations in electronically excited poly(para-phenylene) are
studied using many-body perturbation theory and density-functional-theory
methods. A sophisticated description of the electron-hole interaction is
required to describe the energies of the excitonic states, but we show that the
structural relaxations associated with exciton formation can be obtained quite
accurately within a constrained density-functional-theory approach. We find
that the structural relaxations in the low-energy excitonic states extend over
about 8 monomers, leading to an energy reduction of 0.22 eV and a Stokes shift
of 0.40 eV.Comment: 4 pages, 3 figure
Dynamical bi-stability of single-molecule junctions: A combined experimental/theoretical study of PTCDA on Ag(111)
The dynamics of a molecular junction consisting of a PTCDA molecule between
the tip of a scanning tunneling microscope and a Ag(111) surface have been
investigated experimentally and theoretically. Repeated switching of a PTCDA
molecule between two conductance states is studied by low-temperature scanning
tunneling microscopy for the first time, and is found to be dependent on the
tip-substrate distance and the applied bias. Using a minimal model Hamiltonian
approach combined with density-functional calculations, the switching is shown
to be related to the scattering of electrons tunneling through the junction,
which progressively excite the relevant chemical bond. Depending on the
direction in which the molecule switches, different molecular orbitals are
shown to dominate the transport and thus the vibrational heating process. This
in turn can dramatically affect the switching rate, leading to non-monotonic
behavior with respect to bias under certain conditions. In this work, rather
than simply assuming a constant density of states as in previous works, it was
modeled by Lorentzians. This allows for the successful description of this
non-monotonic behavior of the switching rate, thus demonstrating the importance
of modeling the density of states realistically.Comment: 20 pages, 6 figures, 1 tabl
Doppler Shift in Andreev Reflection from a Moving Superconducting Condensate in Nb/InAs Josephson Junctions
We study narrow ballistic Josephson weak links in a InAs quantum wells
contacted by Nb electrodes and find a dramatic magnetic-field suppression of
the Andreev reflection amplitude, which occurs even for in-plane field
orientation with essentially no magnetic flux through the junction. Our
observations demonstrate the presence of a Doppler shift in the energy of the
Andreev levels, which results from diamagnetic screening currents in the hybrid
Nb/InAs-banks. The data for conductance, excess and critical currents can be
consistently explained in terms of the sample geometry and the McMillan energy,
characterizing the transparency of the Nb/InAs-interface.Comment: 4 pages, 5 figures, title modifie
Excitonic Effects on Optical Absorption Spectra of Doped Graphene
We have performed first-principles calculations to study optical absorption
spectra of doped graphene with many-electron effects included. Both self-energy
corrections and electron-hole interactions are reduced due to the enhanced
screening in doped graphene. However, self-energy corrections and excitonic
effects nearly cancel each other, making the prominent optical absorption peak
fixed around 4.5 eV under different doping conditions. On the other hand, an
unexpected increase of the optical absorbance is observed within the infrared
and visible-light frequency regime (1 ~ 3 eV). Our analysis shows that a
combining effect from the band filling and electron-hole interactions results
in such an enhanced excitonic effect on the optical absorption. These unique
variations of the optical absorption of doped graphene are of importance to
understand relevant experiments and design optoelectronic applications.Comment: 15 pages, 5 figures; Nano Lett., Article ASAP (2011
Optical absorption spectra of finite systems from a conserving Bethe-Salpeter equation approach
We present a method for computing optical absorption spectra by means of a
Bethe-Salpeter equation approach, which is based on a conserving linear
response calculation for electron-hole coherences in the presence of an
external electromagnetic field. This procedure allows, in principle, for the
determination of the electron-hole correlation function self-consistently with
the corresponding single-particle Green function. We analyze the general
approach for a "one-shot" calculation of the photoabsorption cross section of
finite systems, and discuss the importance of scattering and dephasing
contributions in this approach. We apply the method to the closed-shell
clusters Na_4, Na^+_9 and Na^+_(21), treating one active electron per Na atom.Comment: 9 pages, 3 figure
Molecular geometry optimization with a genetic algorithm
We present a method for reliably determining the lowest energy structure of
an atomic cluster in an arbitrary model potential. The method is based on a
genetic algorithm, which operates on a population of candidate structures to
produce new candidates with lower energies. Our method dramatically outperforms
simulated annealing, which we demonstrate by applying the genetic algorithm to
a tight-binding model potential for carbon. With this potential, the algorithm
efficiently finds fullerene cluster structures up to starting
from random atomic coordinates.Comment: 4 pages REVTeX 3.0 plus 3 postscript figures; to appear in Physical
Review Letters. Additional information available under "genetic algorithms"
at http://www.public.iastate.edu/~deaven
Ab-initio calculation of the electronic and optical excitations in polythiophene: effects of intra- and interchain screening
We present an calculation of the electronic and optical excitations of an
isolated polythiophene chain as well as of bulk polythiophene. We use the GW
approximation for the electronic self-energy and include excitonic effects by
solving the electron-hole Bethe-Salpeter equation. The inclusion of interchain
screening in the case of bulk polythiophene drastically reduces both the
quasi-particle band gap and the exciton binding energies, but the optical gap
is hardly affected. This finding is relevant for conjugated polymers in
general.Comment: 4 pages, 1 figur
- …