125 research outputs found
Simulating STM transport in alkanes from first principles
Simulations of scanning tunneling microscopy measurements for molecules on
surfaces are traditionally based on a perturbative approach, most typically
employing the Tersoff-Hamann method. This assumes that the STM tip is far from
the sample so that the two do not interact with each other. However, when the
tip gets close to the molecule to perform measurements, the electrostatic
interplay between the tip and substrate may generate non-trivial potential
distribution, charge transfer and forces, all of which may alter the electronic
and physical structure of the molecule. These effects are investigated with the
ab initio quantum transport code SMEAGOL, combining non-equilibrium Green's
functions formalism with density functional theory. In particular, we
investigate alkanethiol molecules terminated with either CH3 or CF3 end-groups
on gold surfaces, for which recent experimental data are available. We discuss
the effects connected to the interaction between the STM tip and the molecule,
as well as the asymmetric charge transfer between the molecule and the
electrodes.Comment: 10 pages, 18 figure
Efficient atomic self-interaction correction scheme for non-equilibrium quantum transport
Density functional theory calculations of electronic transport based on local
exchange and correlation functionals contain self-interaction errors. These
originate from the interaction of an electron with the potential generated by
itself and may be significant in metal-molecule-metal junctions due to the
localized nature of the molecular orbitals. As a consequence, insulating
molecules in weak contact with metallic electrodes erroneously form highly
conducting junctions, a failure similar to the inability of local functionals
of describing Mott-Hubbard insulators. Here we present a fully self-consistent
and still computationally undemanding self-interaction correction scheme that
overcomes these limitations. The method is implemented in the Green's function
non-equilibrium transport code Smeagol and applied to the prototypical cases of
benzene molecules sandwiched between gold electrodes. The self-interaction
corrected Kohn-Sham highest occupied molecular orbital now reproduces closely
the negative of the molecular ionization potential and is moved away from the
gold Fermi energy. This leads to a drastic reduction of the low bias current in
much better agreement with experiments.Comment: 4 pages, 5 figure
AFLOW-QHA3P: Robust and automated method to compute thermodynamic properties of solids
Accelerating the calculations of finite-temperature thermodynamic properties is a major challenge for rational materials design. Reliable methods can be quite expensive, limiting their applicability in autonomous high-throughput workflows. Here, the three-phonon quasiharmonic approximation (QHA) method is introduced, requiring only three phonon calculations to obtain a thorough characterization of the material. Leveraging a Taylor expansion of the phonon frequencies around the equilibrium volume, the method efficiently resolves the volumetric thermal expansion coefficient, specific heat at constant pressure, the enthalpy, and bulk modulus. Results from the standard QHA and experiments corroborate the procedure, and additional comparisons are made with the recently developed self-consistent QHA. The three approaches—three-phonon, standard, and self-consistent QHAs—are all included within the open-source ab initio framework aflow, allowing the automated determination of properties with various implementations within the same framework
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
Electronic structure of the Au/benzene-1,4-dithiol/Au transport interface: Effects of chemical bonding
We present results of electronic structure calculations for well-relaxed
Au/benzene-1,4-dithiol/Au molecular contacts, based on density functional
theory and the generalized gradient approximation. Electronic states in the
vicinity of the Fermi energy are mainly of Au 5d and S 3p symmetry, whereas
contributions of C 2p states are very small. Hybridization between C 2p
orbitals within the benzene substructure is strongly suppressed due to S-C
bonding. In agreement with experimental findings, this corresponds to a
significantly reduced conductance of the molecular contact.Comment: 7 pages, 5 figures, accepted by Chemical Physics Letter
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
Self-interaction errors in density functional calculations of electronic transport
All density functional calculations of single-molecule transport to date have
used continuous exchange-correlation approximations. The lack of derivative
discontinuity in such calculations leads to the erroneous prediction of
metallic transport for insulating molecules. A simple and computationally
undemanding atomic self-interaction correction greatly improves the agreement
with experiment for the prototype Au/dithiolated-benzene/Au junction.Comment: 4 pages. Also available at http://www.smeagol.tcd.i
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