110 research outputs found
Undoing static correlation: Long-range charge transfer in time-dependent density functional theory
Long-range charge transfer excited states are notoriously badly
underestimated in time-dependent density functional theory (TDDFT). We resolve
how {\it exact} TDDFT captures charge transfer between open-shell species: in
particular the role of the step in the ground-state potential, and the severe
frequency-dependence of the exchange-correlation kernel. An expression for the
latter is derived, that becomes exact in the limit that the charge-transfer
excitations are well-separated from other excitations. The exchange-correlation
kernel has the task of undoing the static correlation in the ground state
introduced by the step, in order to accurately recover the physical
charge-transfer states.Comment: 2 figure
Electrical response of molecular systems: the power of self-interaction corrected Kohn-Sham theory
The accurate prediction of electronic response properties of extended
molecular systems has been a challenge for conventional, explicit density
functionals. We demonstrate that a self-interaction correction implemented
rigorously within Kohn-Sham theory via the Optimized Effective Potential (OEP)
yields polarizabilities close to the ones from highly accurate
wavefunction-based calculations and exceeding the quality of
exact-exchange-OEP. The orbital structure obtained with the OEP-SIC functional
and approximations to it are discussed.Comment: accepted for publication in Physical Review Letter
Charge-transfer in time-dependent density-functional theory via spin-symmetry-breaking
Long-range charge-transfer excitations pose a major challenge for
time-dependent density functional approximations. We show that
spin-symmetry-breaking offers a simple solution for molecules composed of
open-shell fragments, yielding accurate excitations at large separations when
the acceptor effectively contains one active electron. Unrestricted
exact-exchange and self-interaction-corrected functionals are performed on
one-dimensional models and the real LiH molecule within the pseudopotential
approximation to demonstrate our results.Comment: 5 pages, 4 figure
Local correlation functional for electrons in two dimensions
We derive a local approximation for the correlation energy in two-dimensional
electronic systems. In the derivation we follow the scheme originally developed
by Colle and Salvetti for three dimensions, and consider a Gaussian
approximation for the pair density. Then, we introduce an ad-hoc modification
which better accounts for both the long-range correlation, and the
kinetic-energy contribution to the correlation energy. The resulting functional
is local, and depends parametrically on the number of electrons in the system.
We apply this functional to the homogeneous electron gas and to a set of
two-dimensional quantum dots covering a wide range of electron densities and
thus various amounts of correlation. In all test cases we find an excellent
agreement between our results and the exact correlation energies. Our
correlation functional has a form that is simple and straightforward to
implement, but broadly outperforms the commonly used local-density
approximation
Novel properties of the Kohn-Sham exchange potential for open systems: application to the two-dimensional electron gas
The properties of the Kohn-Sham (KS) exchange potential for open systems in
thermodynamical equilibrium, where the number of particles is non-conserved,
are analyzed with the Optimized Effective Potential (OEP) method of Density
Functional Theory (DFT) at zero temperature. The quasi two-dimensional electron
gas (2DEG) is used as an illustrative example. The main findings are that the
KS exchange potential builds a significant barrier-like structure under slight
population of the second subband, and that both the asymptotic value of the KS
exchange potential and the inter-subband energy jump discontinuously at the
one-subband (1S) -> two-subband (2S) transition. The results obtained in this
system offer new insights on open problems of semiconductors, such as the
band-gap underestimation and the band-gap renormalization by photo-excited
carriers.Comment: 7 pages, 3 figures, uses epl.cls(included), accepted for publication
in Europhysics Letter
Optimized Effective Potential Method in Current-Spin Density Functional Theory
Current-spin density functional theory (CSDFT) provides a framework to
describe interacting many-electron systems in a magnetic field which couples to
both spin- and orbital-degrees of freedom. Unlike in usual (spin-) density
functional theory, approximations to the exchange-correlation energy based on
the model of the uniform electron gas face problems in practical applications.
In this work, explicitly orbital-dependent functionals are used and a
generalization of the Optimized Effective Potential (OEP) method to the CSDFT
framework is presented. A simplifying approximation to the resulting integral
equations for the exchange-correlation potentials is suggested. A detailed
analysis of these equations is carried out for the case of open-shell atoms and
numerical results are given using the exact-exchange energy functional. For
zero external magnetic field, a small systematic lowering of the total energy
for current-carrying states is observed due to the inclusion of the current in
the Kohn-Sham scheme. For states without current, CSDFT results coincide with
those of spin density functional theory.Comment: 11 pages, 3 figure
Exchange-correlation orbital functionals in current-density-functional theory: Application to a quantum dot in magnetic fields
The description of interacting many-electron systems in external magnetic
fields is considered in the framework of the optimized effective potential
method extended to current-spin-density functional theory. As a case study, a
two-dimensional quantum dot in external magnetic fields is investigated.
Excellent agreement with quantum Monte Carlo results is obtained when
self-interaction corrected correlation energies from the standard local
spin-density approximation are added to exact-exchange results. Full
self-consistency within the complete current-spin-density-functional framework
is found to be of minor importance.Comment: 5 pages, 2 figures, submitted to PR
Delta Self-Consistent Field as a method to obtain potential energy surfaces of excited molecules on surfaces
We present a modification of the SCF method of calculating energies
of excited states, in order to make it applicable to resonance calculations of
molecules adsorbed on metal surfaces, where the molecular orbitals are highly
hybridized. The SCF approximation is a density functional method
closely resembling standard density functional theory (DFT), the only
difference being that in SCF one or more electrons are placed in higher
lying Kohn-Sham orbitals, instead of placing all electrons in the lowest
possible orbitals as one does when calculating the ground state energy within
standard DFT. We extend the SCF method by allowing excited electrons to
occupy orbitals which are linear combinations of Kohn-Sham orbitals. With this
extra freedom it is possible to place charge locally on adsorbed molecules in
the calculations, such that resonance energies can be estimated. The method is
applied to N, CO and NO adsorbed on different metallic surfaces and
compared to ordinary SCF without our modification, spatially
constrained DFT and inverse-photoemission spectroscopy (IPES) measurements.
This comparison shows that the modified SCF method gives results in
close agreement with experiment, significantly closer than the comparable
methods. For N adsorbed on ruthenium (0001) we map out a 2-dimensional part
of the potential energy surfaces in the ground state and the 2-resonance.
Finally we compare the SCF approach on gas-phase N and CO, to
higher accuracy methods. Excitation energies are approximated with accuracy
close to that of time-dependent density functional theory, and we see very good
agreement in the minimum shift of the potential energy surfaces in the excited
state compared to the ground state.Comment: 11 pages, 7 figure
Excitations in time-dependent density-functional theory
An approximate solution to the time-dependent density functional theory
(TDDFT) response equations for finite systems is developed, yielding
corrections to the single-pole approximation. These explain why allowed
Kohn-Sham transition frequencies and oscillator strengths are usually good
approximations to the true values, and why sometimes they are not. The
approximation yields simple expressions for G\"orling-Levy perturbation theory
results, and a method for estimating expectation values of the unknown
exchange-correlation kernel.Comment: 4 pages, 1 tabl
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