25 research outputs found
Driven Liouville von Neumann Approach for Time-Dependent Electronic Transport Calculations in a Nonorthogonal Basis-Set Representation
A nonorthogonal localized basis-set
implementation of the driven
Liouville von Neumann (DLvN) approach is presented. The method is
based on block-orthogonalization of the Hamiltonian and overlap matrix
representations, yielding nonoverlapping blocks that correspond to
the various system sections. An extended HuÌckel description
of gold/benzene-dithiol/gold and gold/pyridine-dithiol/gold junctions
is used to demonstrate the performance of the method. The presented
generalization is an important milestone toward using the DLvN approach
for performing accurate dynamic electronic transport calculations
in realistic model systems, based on density functional theory packages
that rely on atom-centered basis-set representations
Pair-Wise and Many-Body Dispersive Interactions Coupled to an Optimally Tuned Range-Separated Hybrid Functional
We
propose a nonempirical, pair-wise or many-body dispersion-corrected,
optimally tuned range-separated hybrid functional. This functional
retains the advantages of the optimal-tuning approach in the prediction
of the electronic structure. At the same time, it gains accuracy in
the prediction of binding energies for dispersively bound systems,
as demonstrated on the S22 and S66 benchmark sets of weakly bound
dimers
Reliable Prediction of Charge Transfer Excitations in Molecular Complexes Using Time-Dependent Density Functional Theory
Reliable Prediction of Charge Transfer Excitations in Molecular Complexes Using Time-Dependent Density Functional Theor
Low-Energy Charge-Transfer Excitons in Organic Solids from First-Principles: The Case of Pentacene
The nature of low energy optical
excitations, or excitons, in organic
solids is of central relevance to many optoelectronic applications,
including solar energy conversion. Excitons in solid pentacene, a
prototypical organic semiconductor, have been the subject of many
experimental and theoretical studies, with differing conclusions as
to the degree of their charge-transfer character. Using first-principles
calculations based on density functional theory and many-body perturbation
theory, we compute the average electronâhole distance and quantify
the degree of charge-transfer character within optical excitations
in solid-state pentacene. We show that several low-energy singlet
excitations are characterized by a weak overlap between electron and
hole and an average electronâhole distance greater than 6 Ă
.
Additionally, we show that the character of the lowest-lying singlet
and triplet excitons is well-described with a simple analytic envelope
function of the electronâhole distance
Interlayer Potential for Homogeneous Graphene and Hexagonal Boron Nitride Systems: Reparametrization for Many-Body Dispersion Effects
A new
parametrization of the anisotropic interlayer potential for
hexagonal boron nitride (<i>h</i>-BN ILP) is presented.
The force-field is benchmarked against density functional theory calculations
of several dimer systems within the Heyd-Scuseria-Ernzerhof hybrid
density functional approximation, corrected for many-body dispersion
effects. The latter, more advanced method for treating dispersion,
is known to produce binding energies nearly twice as small as those
obtained with pairwise correction schemes, used for an earlier ILP
parametrization. The new parametrization yields good agreement with
the reference calculations to within âŒ1 and âŒ0.5 meV/atom
for binding and sliding energies, respectively. For completeness,
we present a complementary parameter set for homogeneous graphitic
systems. Together with our previously suggested ILP parametrization
for the heterogeneous graphene/<i>h</i>-BN junction, this
provides a powerful tool for consistent simulation of the structural,
mechanical, tribological, and heat transport properties of both homogeneous
and heterogeneous layered structures based on graphene and <i>h</i>-BN
Interlayer Potential for Graphene/<i>h</i>âBN Heterostructures
We present a new
force-field potential that describes the interlayer
interactions in heterojunctions based on graphene and hexagonal boron
nitride (<i>h</i>-BN). The potential consists of a long-range
attractive term and a short-range anisotropic repulsive term. Its
parameters are calibrated against reference binding and sliding energy
profiles for a set of finite dimer systems and the periodic graphene/<i>h</i>-BN bilayer, obtained from density functional theory using
a screened-exchange hybrid functional augmented by a many-body dispersion
treatment of long-range correlation. Transferability of the parametrization
is demonstrated by considering the binding energy of bulk graphene/<i>h</i>-BN alternating stacks. Benchmark calculations for the
superlattice formed when relaxing the supported periodic heterogeneous
bilayer provide good agreement with both experimental results and
previous computational studies. For a free-standing bilayer we predict
a highly corrugated relaxed structure. This, in turn, is expected
to strongly alter the physical properties of the underlying monolayers.
Our results demonstrate the potential of the developed force-field
to model the structural, mechanical, tribological, and dynamic properties
of layered heterostructures based on graphene and <i>h</i>-BN
Curvature and Frontier Orbital Energies in Density Functional Theory
Perdew et al. discovered two different properties of
exact KohnâSham
density functional theory (DFT): (i) The exact total energy versus
particle number is a series of linear segments between integer electron
points. (ii) Across an integer number of electrons, the exchange-correlation
potential âjumpsâ by a constant, known as the derivative
discontinuity (DD). Here we show analytically that in both the original
and the generalized KohnâSham formulation of DFT the two properties
are two sides of the same coin. The absence of a DD dictates deviation
from piecewise linearity, but the latter, appearing as curvature,
can be used to correct for the former, thereby restoring the physical
meaning of orbital energies. A simple correction scheme for any semilocal
and hybrid functional, even HartreeâFock theory, is shown to
be effective on a set of small molecules, suggesting a practical correction
for the infamous DFT gap problem. We show that optimally tuned range-separated
hybrid functionals can inherently minimize <i>both</i> DD
and curvature, thus requiring no correction, and that this can be
used as a sound theoretical basis for novel tuning strategies
Enhanced Magnetoresistance in Molecular Junctions by Geometrical Optimization of Spin-Selective Orbital Hybridization
Molecular junctions based on ferromagnetic
electrodes allow the study of electronic spin transport near the limit
of spintronics miniaturization. However, these junctions reveal moderate
magnetoresistance that is sensitive to the orbital structure at their
ferromagnetâmolecule interfaces. The key structural parameters
that should be controlled in order to gain high magnetoresistance
have not been established, despite their importance for efficient
manipulation of spin transport at the nanoscale. Here, we show that
single-molecule junctions based on nickel electrodes and benzene molecules
can yield a significant anisotropic magnetoresistance of up to âŒ200%
near the conductance quantum <i>G</i><sub>0</sub>. The measured
magnetoresistance is mechanically tuned by changing the distance between
the electrodes, revealing a nonmonotonic response to junction elongation.
These findings are ascribed with the aid of first-principles calculations
to variations in the metalâmolecule orientation that can be
adjusted to obtain highly spin-selective orbital hybridization. Our
results demonstrate the important role of geometrical considerations
in determining the spin transport properties of metalâmolecule
interfaces
Molecule-Adsorbed Topological Insulator and Metal Surfaces: A Comparative First-Principles Study
We
compare electronic structure characteristics of three different
kinds of benzene-adsorbed (111) surfaces: that of Bi<sub>2</sub>Te<sub>3</sub>, a prototypical topological insulator, that of Au, a prototypical
inert metal, and that of Pt, a prototypical catalytic metal. Using
first-principles calculations based on dispersion-corrected density
functional theory, we show that benzene is chemisorbed on Pt, but
physisorbed on Au and Bi<sub>2</sub>Te<sub>3</sub>. The adsorption
on Bi<sub>2</sub>Te<sub>3</sub> is particularly weak, consistent with
a minimal perturbation of the electronic structure at the surface
of the topological insulator, revealed by a detailed analysis of the
interaction of the molecular orbitals with the topological surface
states
Why Are Diphenylalanine-Based Peptide Nanostructures so Rigid? Insights from First Principles Calculations
The diphenylalanine peptide self-assembles
to form nanotubular
structures of remarkable mechanical, piezolelectrical, electrical,
and optical properties. The tubes are unexpectedly stiff, with reported
Youngâs moduli of 19â27 GPa that were extracted using
two independent techniques. Yet the physical basis for the remarkable
rigidity is not fully understood. Here, we calculate the Youngâs
modulus for bulk diphenylalanine peptide from first principles, using
density functional theory with dispersive corrections. The calculation
demonstrates that at least half of the stiffness of the material is
the result of dispersive interactions. We further quantify the nature
of various inter- and intramolecular interactions. We reveal that
despite the porous nature of the lattice, there is an array of rigid
nanotube backbones with interpenetrating âzipper-likeâ
aromatic interlocks that result in stiffness and robustness. This
presents a general strategy for the analysis of bioinspired functional
materials and may pave the way for rational design of bionanomaterials