925 research outputs found
Quantum fluid-dynamics from density functional theory
A partial differential eigenvalue equation for the density displacement
fields associated with electronic excitations is derived in the framework of
density functional theory. Our quantum fluid-dynamical approach is based on a
variational principle and the Kohn-Sham ground-state energy functional, using
only the occupied Kohn-Sham orbitals. It allows for an intuitive interpretation
of electronic excitations in terms of intrinsic local currents that obey a
continuity equation. We demonstrate the capabilities of this non-empirical
approach by calculating the photoabsorption spectra of small sodium clusters.
The quantitative agreement between theoretical and experimental spectra shows
that even for the smallest clusters, the resonances observed experimentally at
low temperatures can be interpreted in terms of density vibrations.Comment: RevTeX file with 2 figures. Update on April 17 2001: Typos corrected,
references updated, larger axes labels on Fig. 1. Accepted for publication in
Phys. Rev.
Collectivity in the optical response of small metal clusters
The question whether the linear absorption spectra of metal clusters can be
interpreted as density oscillations (collective ``plasmons'') or can only be
understood as transitions between distinct molecular states is still a matter
of debate for clusters with only a few electrons. We calculate the
photoabsorption spectra of Na2 and Na5+ comparing two different methods:
quantum fluid-dynamics and time-dependent density functional theory. The
changes in the electronic structure associated with particular excitations are
visualized in ``snapshots'' via transition densities. Our analysis shows that
even for the smallest clusters, the observed excitations can be interpreted as
intuitively understandable density oscillations. For Na5+, the importance of
self-interaction corrections to the adiabatic local density approximation is
demonstrated.Comment: 6 pages, 3 figures. To appear in special issue of Applied Physics B,
"Optical properties of Nanoparticles
On the challenge to improve the density response with unusual gradient approximations
Certain excitations, especially ones of long-range charge transfer character,
are poorly described by time-dependent density functional theory (TDDFT) when
typical (semi-)local functionals are used. A proper description of these
excitations would require an exchange-correlation response differing
substantially from the usual (semi-)local one. It has recently been shown that
functionals of the generalized gradient approximation (GGA) type can yield
unusual potentials, mimicking features of the exact exchange derivative
discontinuity and showing divergences on orbital nodal surfaces. We here
investigate whether these unusual potential properties translate into
beneficial response properties. Using the Sternheimer formalism we closely
investigate the response obtained with the 2013 exchange approximation by
Armiento and K\"ummel (AK13) and the 1988 exchange approximation by Becke
(B88), both of which show divergences on orbital nodal planes. Numerical
calculations for Na2 as well as analytical and numerical calculations for the
hydrogen atom show that the response of AK13 behaves qualitatively different
from usual semi local functionals. However, the AK13 functional leads to
fundamental instabilities in the asymptotic region that prevent its practical
application in TDDFT. Our findings may help the development of future improved
functionals, and corroborate that the frequency-dependent Sternheimer formalism
is excellently suited for running and analyzing TDDFT calculations
Static Electric Dipole Polarizabilities of Na Clusters
The static electric dipole polarizability of clusters with
even N has been calculated in a collective, axially averaged and a
three-dimensional, finite-field approach for , including the
ionic structure of the clusters. The validity of a collective model for the
static response of small systems is demonstrated. Our density functional
calculations verify the trends and fine structure seen in a recent experiment.
A pseudopotential that reproduces the experimental bulk bond length and atomic
energy levels leads to a substantial increase in the calculated
polarizabilities, in better agreement with experiment. We relate remaining
differences in the magnitude of the theoretical and experimental
polarizabilities to the finite temperature present in the experiments.Comment: 7 pages, 3 figures, accepted for publication in the European Physical
Journal
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
Simple iterative construction of the optimized effective potential for orbital functionals, including exact exchange
For exchange-correlation functionals that depend explicitly on the Kohn-Sham
orbitals, the potential V_{\mathrm{xc}\sigma}(\re) must be obtained as the
solution of the optimized effective potential (OEP) integral equation. This is
very demanding and has limited the use of orbital functionals like exact
exchange. We demonstrate that the OEP can be obtained iteratively by solving a
system of partial differential equations instead of an integral equation. This
amounts to calculating the orbital shifts that exactify the Krieger-Li-Iafrate
(KLI) approximation. Unoccupied orbitals do not need to be calculated. Accuracy
and efficiency of the method are shown for atoms and clusters using the exact
exchange energy. Counter-intuitive asymptotic limits of the exact OEP, not
accessible from previous constructions, are presented.Comment: Physical Review Letters, accepted for publication. 4 pages, 1 figur
Dynamics of conversion of supercurrents into normal currents, and vice versa
The generation and destruction of the supercurrent in a superconductor (S)
between two resistive normal (N) current leads connected to a current source is
computed from the source equation for the supercurrent density. This equation
relates the gradient of the pair potential's phase to electron and hole
wavepackets that create and destroy Cooper pairs in the N/S interfaces. Total
Andreev reflection and supercurrent transmission of electrons and holes are
coupled together by the phase rigidity of the non-bosonic Cooper-pair
condensate. The calculations are illustrated by snapshots from a computer film.Comment: 8 pages, 1 figure, accepted by Phys. Rev.
Measurement properties of the German version of the IKDC subjective knee form (IKDC-SKF).
PURPOSE: To examine the measurement properties of the German International Knee Documentation Committee Subjective Knee Form (IKDC-SKF) in knee disorder patients. METHODS: Three hundred twelve consecutive patients undergoing surgery for anterior cruciate ligament, meniscus and/or cartilage injuries completed the IKDC-SKF, Lysholm Score, Tegner Activity Scale, and Short Form-12 Health Survey before and 6 months post-surgery. IKDC-SKF measurement properties were calculated and patients were also asked to rate the relevance/comprehensibility of the questionnaire items. RESULTS: Reliability was good with high Cronbach's alpha and intraclass correlation coefficients, and standard error of measurement values of 4.4 to 6.0. The smallest detectable change (SDC) ranged from 12.3 to 16.7 points. Validity was good with 90% of all hypotheses confirmed. Confirmatory factor analysis did not show adequate fitting indices within the model. Over half of the items were rated as essential, and all were well comprehended. The majority of hypotheses for responsiveness were confirmed. No floor and ceiling effects were observed. The area under the curve ranged from 0.82 to 0.89 and the minimal important difference was smaller than the SDC. CONCLUSIONS: The German IKDC-SKF is a reliable outcome measure with good hypotheses testing and responsiveness, but its MIC and structural/content validity need further analysis
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