Correlation energy functional and potential from time-dependent exact-exchange theory

In this work we have studied a new functional for the correlation energy obtained from the exact-exchange (EXX) approximation within time-dependent density functional theory (TDDFT). Correlation energies have been calculated for a number of different atoms showing excellent agreement with results from more sophisticated methods. These results loose little accuracy by approximating the EXX kernel by its static value, a procedure which enormously simplifies the calculations. The correlation potential, obtained by taking the functional derivative with respect to the density, turns out to be remarkably accurate for all atoms studied. This potential has been used to calculate ionization potentials, static polarizabilities and van der Waals coefficients with results in close agreement with experiment.Comment: 6 pages, 2 figure

Fluctuating parts of nuclear ground state correlation energies

Background: Heavy atomic nuclei are often described using the Hartree-Fock-Bogoliubov (HFB) method. In principle, this approach takes into account Pauli effects and pairing correlations while other correlation effects are mimicked through the use of effective density-dependent interactions. Purpose: Investigate the influence of higher order correlation effects on nuclear binding energies using Skyrme's effective interaction. Methods: A cut-off in relative momenta is introduced in order to remove ultraviolet divergences caused by the zero-range character of the interaction. Corrections to binding energies are then calculated using the quasiparticle-random-phase approximation (QRPA) and second order many-body perturbation theory (MBPT2). Result: Contributions to the correlation energies are evaluated for several isotopic chains and an attempt is made to disentangle which parts give rise to fluctuations that may be difficult to incorporate on the HFB level. The dependence of the results on the cut-off is also investigated. Conclusions: The improved interaction allows explicit summations of perturbation series which is useful for the description of some nuclear observables. However, refits of the interaction parameters are needed to obtain more quantitative results

The correlation potential in density functional theory at the GW-level: spherical atoms

As part of a project to obtain better optical response functions for nano materials and other systems with strong excitonic effects we here calculate the exchange-correlation (XC) potential of density-functional theory (DFT) at a level of approximation which corresponds to the dynamically- screened-exchange or GW approximation. In this process we have designed a new numerical method based on cubic splines which appears to be superior to other techniques previously applied to the "inverse engineering problem" of DFT, i.e., the problem of finding an XC potential from a known particle density. The potentials we obtain do not suffer from unphysical ripple and have, to within a reasonable accuracy, the correct asymptotic tails outside localized systems. The XC potential is an important ingredient in finding the particle-conserving excitation energies in atoms and molecules and our potentials perform better in this regard as compared to the LDA potential, potentials from GGA:s, and a DFT potential based on MP2 theory.Comment: 13 pages, 9 figure

Dynamical effects in X-ray spectra and the final-state rule

The dynamical theory of X-ray spectra due to Nozieres and De Dominicis (ND, 1969) is evaluated here numerically for numerous model systems including cases where the core-hole potential possesses a bound state. It is shown that the resulting emission spectra obey the final-state rule rather accurately. An approximate but analytical derivation of this rule is given which provides insight into the mechanisms leading to the final-state rule. The evaluations are performed with the use of two methods, one based on an integral equation together with a separable core-hole potential and the other based on determinantal wave functions for a finite number (N) of electrons in a box. The equivalence of the two methods is demonstrated both formally and numerically. By comparing them the authors prove the finite-N approach to be accurate already for rather small N. They also show that a separable potential does not give rise to any spurious results but can actually be chosen to yield the same ND spectrum as a local potential. The ND theory of X-ray photoemission spectra is discussed and from calculations of the exponent function α(ω) for several model systems closely corresponding to simple metals the authors conclude the equivalence of this theory and its asymptotic approximation as far as the extraction of asymmetry indices is concerned. Recent criticism of the major conclusions reached here and in previous work is refuted.(61 refs

Exact-exchange kernel of time-dependent density functional theory: Frequency dependence and photoabsorption spectra of atoms

In this work we have calculated excitation energies and photoionization cross sections of Be and Ne in the exact-exchange (EXX) approximation of time-dependent density functional theory (TDDFT). The main focus has been on the frequency dependence of the EXX kernel and on how it affects the spectrum as compared to the corresponding adiabatic approximation. We show that for some discrete excitation energies the frequency dependence is essential to reproduce the results of time-dependent Hartree-Fock theory. Unfortunately, we have found that the EXX approximation breaks down completely at higher energies, producing a response function with the wrong analytic structure and making inner-shell excitations disappear from the calculated spectra. We have traced this failure to the existence of vanishing eigenvalues of the Kohn-Sham non-interacting response function. Based on the adiabatic TDDFT formalism we propose a new way of deriving the Fano parameters of autoionizing resonances.Comment: 14 pages, 7 figure

Calculations of Hubbard U from first-principles

The Hubbard \emph{U} of the \emph{3d} transition metal series as well as SrVO$_{3}$, YTiO$_{3}$, Ce and Gd has been estimated using a recently proposed scheme based on the random-phase approximation. The values obtained are generally in good accord with the values often used in model calculations but for some cases the estimated values are somewhat smaller than those used in the literature. We have also calculated the frequency-dependent \emph{U} for some of the materials. The strong frequency dependence of \emph{U} in some of the cases considered in this paper suggests that the static value of \emph{U} may not be the most appropriate one to use in model calculations. We have also made comparison with the constrained LDA method and found some discrepancies in a number of cases. We emphasize that our scheme and the constrained LDA method theoretically ought to give similar results and the discrepancies may be attributed to technical difficulties in performing calculations based on currently implemented constrained LDA schemes.Comment: 24 pages, 13 figures; Submitted to Phys. Rev.

A simple, efficient, and general treatment of the singularities in Hartree-Fock and exact-exchange Kohn-Sham methods for solids

We present a general scheme for treating the integrable singular terms within exact exchange (EXX) Kohn-Sham or Hartree-Fock (HF) methods for periodic solids. We show that the singularity corrections for treating these divergencies depend only on the total number and the positions of k-points and on the lattice vectors, in particular the unit cell volume, but not on the particular positions of atoms within the unit cell. The method proposed here to treat the singularities constitutes a stable, simple to implement, and general scheme that can be applied to systems with arbitrary lattice parameters within either the EXX Kohn-Sham or the HF formalism. We apply the singularity correction to a typical symmetric structure, diamond, and to a more general structure, trans-polyacetylene. We consider the effect of the singularity corrections on volume optimisations and k-point convergence. While the singularity corrections clearly depends on the total number of k-points, it exhibits a remarkably small dependence upon the choice of the specific arrangement of the k-points.Comment: 24 pages, 5 Figures, re-submitted to Phys. Rev. B after revision