14,173 research outputs found
A natural orbital functional for the many-electron problem
The exchange-correlation energy in Kohn-Sham density functional theory is
expressed as a functional of the electronic density and the Kohn-Sham orbitals.
An alternative to Kohn-Sham theory is to express the energy as a functional of
the reduced first-order density matrix or equivalently the natural orbitals. In
the former approach the unknown part of the functional contains both a kinetic
and a potential contribution whereas in the latter approach it contains only a
potential energy and consequently has simpler scaling properties. We present an
approximate, simple and parameter-free functional of the natural orbitals,
based solely on scaling arguments and the near satisfaction of a sum rule. Our
tests on atoms show that it yields on average more accurate energies and charge
densities than the Hartree Fock method, the local density approximation and the
generalized gradient approximations
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
Stabilized jellium model and structural relaxation effects on the fragmentation energies of ionized silver clusters
Using the stabilized jellium model in two schemes of `relaxed' and `rigid',
we have calculated the dissociation energies and the fission barrier heights
for the binary fragmentations of singly-ionized and doubly-ionized Ag clusters.
In the calculations, we have assumed spherical geometries for the clusters.
Comparison of the fragmentation energies in the two schemes show differences
which are significant in some cases. This result reveals the advantages of the
relaxed SJM over the rigid SJM in dynamical processes such as fragmentation.
Comparing the relaxed SJM results and axperimental data on fragmentation
energies, it is possible to predict the sizes of the clusters just before their
fragmentations.Comment: 9 pages, 12 JPG figure
Ab initio pseudopotential study of Fe, Co, and Ni employing the spin-polarized LAPW approach
The ground-state properties of Fe, Co, and Ni are studied with the
linear-augmented-plane-wave (LAPW) method and norm-conserving pseudopotentials.
The calculated lattice constant, bulk modulus, and magnetic moment with both
the local-spin-density approximation (LSDA) and the generalized gradient
approximation (GGA) are in good agreement with those of all-electron
calculations, respectively. The GGA results show a substantial improvement over
the LSDA results, i.e., better agreement with experiment. The accurate
treatment of the nonlinear core-valence exchange and correlation interaction is
found to be essential for the determination of the magnetic properties of 3d
transition metals. The present study demonstrates the successful application of
the LAPW pseudopotential approach to the calculation of ground-state properties
of magnetic 3d transition metals.Comment: RevTeX, 14 pages, 2 figures in uufiles for
A local density functional for the short-range part of the electron-electron interaction
Motivated by recent suggestions --to split the electron-electron interaction
into a short-range part, to be treated within the density functional theory,
and a long-range part, to be handled by other techniques-- we compute, with a
diffusion Monte Carlo method, the ground-state energy of a uniform electron gas
with a modified, short-range-only electron-electron interaction \erfc(\mu
r)/r, for different values of the cutoff parameter and of the electron
density. After deriving some exact limits, we propose an analytic
representation of the correlation energy which accurately fits our Monte Carlo
data and also includes, by construction, these exact limits, thus providing a
reliable ``short-range local-density functional''.Comment: 7 pages, 3 figure
Dimensional crossover of the exchange-correlation energy at the semilocal level
Commonly used semilocal density functional approximations for the
exchange-correlation energy fail badly when the true two dimensional limit is
approached. We show, using a quasi-two-dimensional uniform electron gas in the
infinite barrier model, that the semilocal level can correctly recover the
exchange-correlation energy of the two-dimensional uniform electron gas. We
derive new exact constraints at the semilocal level for the dimensional
crossover of the exchange-correlation energy and we propose a method to
incorporate them in any exchange-correlation density functional approximation.Comment: 6 pages, 5 figure
Structural models for the Si(553)-Au atomic chain reconstruction
Recent photoemission experiments on the Si(553)-Au reconstruction show a
one-dimensional band with a peculiar ~1/4 filling. This band could provide an
opportunity for observing large spin-charge separation if electron-electron
interactions could be increased. To this end, it is necessary to understand in
detail the origin of this surface band. A first step is the determination of
the structure of the reconstruction. We present here a study of several
structural models using first-principles density functional calculations. Our
models are based on a plausible analogy with the similar and better known
Si(557)-Au surface, and compared against the sole structure proposed to date
for the Si(553)-Au system [Crain JN et al., 2004 Phys. Rev. B 69 125401 ].
Results for the energetics and the band structures are given. Lines for the
future investigation are also sketched
Ab initio Studies of the Possible Magnetism in BN Sheet by Non-magnetic Impurities and Vacancies
We performed first-principles calculations to investigate the possible
magnetism induced by the different concentrations of non-magnetic impurities
and vacancies in BN sheet. The atoms of Be, B, C, N, O, Al and Si are used to
replace either B or N in the systems as impurities. We discussed the changes in
density of states as well as the extent of the spatial distributions of the
defect states, the possible formation of magnetic moments, the magnitude of the
magnetization energies and finally the exchange energies due to the presence of
these defects. It is shown that the magnetization energies tend to increase as
the concentrations of the defects decreases in most of the defect systems which
implies a definite preference of finite magnetic moments. The calculated
exchange energies are in general tiny but not completely insignificant for two
of the studied defect systems, i.e. one with O impurities for N and the other
with B vacancies.Comment: 8 pages, 10 figures, submitted to Phys. Rev.
Atomic self-interaction correction for molecules and solids
We present an atomic orbital based approximate scheme for self-interaction
correction (SIC) to the local density approximation of density functional
theory. The method, based on the idea of Filippetti and Spaldin [Phys. Rev. B
67, 125109 (2003)], is implemented in a code using localized numerical atomic
orbital basis sets and is now suitable for both molecules and extended solids.
After deriving the fundamental equations as a non-variational approximation of
the self-consistent SIC theory, we present results for a wide range of
molecules and insulators. In particular, we investigate the effect of
re-scaling the self-interaction correction and we establish a link with the
existing atomic-like corrective scheme LDA+U. We find that when no re-scaling
is applied, i.e. when we consider the entire atomic correction, the Kohn-Sham
HOMO eigenvalue is a rather good approximation to the experimental ionization
potential for molecules. Similarly the HOMO eigenvalues of negatively charged
molecules reproduce closely the molecular affinities. In contrast a re-scaling
of about 50% is necessary to reproduce insulator bandgaps in solids, which
otherwise are largely overestimated. The method therefore represents a
Kohn-Sham based single-particle theory and offers good prospects for
applications where the actual position of the Kohn-Sham eigenvalues is
important, such as quantum transport.Comment: 16 pages, 7 figure
Exchange-energy functionals for finite two-dimensional systems
Implicit and explicit density functionals for the exchange energy in finite
two-dimensional systems are developed following the approach of Becke and
Roussel [Phys. Rev. A 39, 3761 (1989)]. Excellent agreement for the
exchange-hole potentials and exchange energies is found when compared with the
exact-exchange reference data for the two-dimensional uniform electron gas and
few-electron quantum dots, respectively. Thereby, this work significantly
improves the availability of approximate density functionals for dealing with
electrons in quasi-two-dimensional structures, which have various applications
in semiconductor nanotechnology.Comment: 5 pages, 3 figure
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