88 research outputs found
Van der Waals interactions in DFT made easy by Wannier functions
Ubiquitous Van der Waals interactions between atoms and molecules are
important for many molecular and solid structures. These systems are often
studied from first principles using the Density Functional Theory (DFT).
However, the commonly used DFT functionals fail to capture the essence of Van
der Waals effects. Many attempts to correct for this problem have been
proposed, which are not completely satisfactory because they are either very
complex and computationally expensive or have a basic semiempirical character.
We here describe a novel approach, based on the use of the Maximally-Localized
Wannier functions, that appears to be promising, being simple, efficient,
accurate, and transferable (charge polarization effects are naturally
included). The results of test applications are presented.Comment: submitted to Phys. Rev. Let
Factors influencing the distribution of charge in polar nanocrystals
We perform first-principles calculations of wurtzite GaAs nanorods to explore
the factors determining charge distributions in polar nanostructures. We show
that both the direction and magnitude of the dipole moment of a
nanorod, and its electic field, depend sensitively on how its surfaces are
terminated and do not depend strongly on the spontaneous polarization of the
underlying lattice. We identify two physical mechanisms by which
is controlled by the surface termination, and we show that the excess charge on
the nanorod ends is not strongly localized. We discuss the implications of
these results for tuning nanocrystal properties, and for their growth and
assembly.Comment: Accepted for publication in Phys. Rev. B Rapid Communication
Projector self-consistent DFT+U using non-orthogonal generalized Wannier functions
We present a formulation of the density-functional theory + Hubbard model
(DFT+U) method that is self-consistent over the choice of Hubbard projectors
used to define the correlated subspaces. In order to overcome the arbitrariness
in this choice, we propose the use of non-orthogonal generalized Wannier
functions (NGWFs) as projectors for the DFT+U correction. We iteratively refine
these NGWF projectors and, hence, the DFT+U functional, such that the
correlated subspaces are fully self-consistent with the DFT+U ground-state. We
discuss the convergence characteristics of this algorithm and compare
ground-state properties thus computed with those calculated using hydrogenic
projectors. Our approach is implemented within, but not restricted to, a
linear-scaling DFT framework, opening the path to DFT+U calculations on systems
of unprecedented size.Comment: 4 pages, 3 figures. This version (v2) matches that accepted for
Physical Review B Rapid Communications on 26th July 201
Bromophenyl functionalization of carbon nanotubes : an ab initio study
We study the thermodynamics of bromophenyl functionalization of carbon
nanotubes with respect to diameter and metallic/insulating character using
density-functional theory (DFT). On one hand, we show that the activation
energy for the grafting of a bromophenyl molecule onto a semiconducting zigzag
nanotube ranges from 0.73 eV to 0.76 eV without any clear trend with respect to
diameter within numerical accuracy. On the other hand, the binding energy of a
single bromophenyl molecule shows a clear diameter dependence and ranges from
1.51 eV for a (8,0) zigzag nanotube to 0.83 eV for a (20,0) zigzag nanotube.
This is in part explained by the transition from sp2 to sp3 bonding occurring
to a carbon atom of a nanotube when a phenyl is grafted to it and the fact that
smaller nanotubes are closer to a sp3 hybridization than larger ones due to
increased curvature. Since a second bromophenyl unit can attach without energy
barrier next to an isolated grafted unit, they are assumed to exist in pairs.
The para configuration is found to be favored for the pairs and their binding
energy decreases with increasing diameter, ranging from 4.34 eV for a (7,0)
nanotube to 2.27 eV for a (29,0) nanotube. An analytic form for this radius
dependence is derived using a tight binding hamiltonian and first order
perturbation theory. The 1/R^2 dependance obtained (where R is the nanotube
radius) is verified by our DFT results within numerical accuracy. Finally,
metallic nanotubes are found to be more reactive than semiconducting nanotubes,
a feature that can be explained by a non-zero density of states at the Fermi
level for metallic nanotubes.Comment: 7 pages, 5 figures and 3 table
Tracing potential energy surfaces of electronic excitations via their transition origins: application to Oxirane
We show that the transition origins of electronic excitations identified by
quantified natural transition orbital (QNTO) analysis can be employed to
connect potential energy surfaces (PESs) according to their character across a
widerange of molecular geometries. This is achieved by locating the switching
of transition origins of adiabatic potential surfaces as the geometry changes.
The transition vectors for analysing transition origins are provided by linear
response time-dependent density functional theory (TDDFT) calculations under
the Tamm-Dancoff approximation. We study the photochemical CO ring opening of
oxirane as an example and show that the results corroborate the traditional
Gomer-Noyes mechanism derived experimentally. The knowledge of specific states
for the reaction also agrees well with that given by previous theoretical work
using TDDFT surface-hopping dynamics that was validated by high-quality quantum
Monte Carlo calculations. We also show that QNTO can be useful for considerably
larger and more complex systems: by projecting the excitations to those of a
reference oxirane molecule, the approach is able to identify and analyse
specific excitations of a trans-2,3-diphenyloxirane molecule.Comment: 14 pages, 12 figure
Vanadium dioxide : A Peierls-Mott insulator stable against disorder
Vanadium dioxide undergoes a first order metal-insulator transition at 340 K.
In this work, we develop and carry out state of the art linear scaling DFT
calculations refined with non-local dynamical mean-field theory. We identify a
complex mechanism, a Peierls-assisted orbital selection Mott instability, which
is responsible for the insulating M phase, and furthermore survives a
moderate degree of disorder.Comment: 5 pages, 4 figures. Supplementary material 8 pages, 4 figures. This
version (v2) matches that accepted for Physical Review Letters on 16th May
201
Linear-scaling DFT+U with full local orbital optimization
We present an approach to the DFT+U method (Density Functional Theory +
Hubbard model) within which the computational effort for calculation of ground
state energies and forces scales linearly with system size. We employ a
formulation of the Hubbard model using nonorthogonal projector functions to
define the localized subspaces, and apply it to a local-orbital DFT method
including in situ orbital optimization. The resulting approach thus combines
linear-scaling and systematic variational convergence. We demonstrate the
scaling of the method by applying it to nickel oxide nano-clusters with sizes
exceeding 7,000 atoms.Comment: 10 pages, 4 figures. This version (v3) matches that accepted for
Physical Review B on 30th January 201
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