LAPW vs. LMTO full-potential simulations and anharmonic dynamics of KNbO3

With the aim to get an insight in the origin of differences in the earlier reported calculation results for KNbO3 and to test the recently proposed implementation of the FP-LMTO method by Methfessel and van Schilfgaarde, we perform a comparative study of the ferroelectric instability in KNbO3 by FP-LMTO and LAPW methods. It is shown that a high precision in the description of the charge density variations over the interstitial region in perovskite materials is essential; the technical limitations of the accuracy of charge-density description apparently accounted for previously reported slight disagreement with the LAPW results. With more accurate description of the charge density by sufficiently fine real-space grid, the results obtained by both methods became almost identical. In order to extract additional information (beyond the harmonic approximation) from the total energy fit obtainable in total-energy calculations, a scheme is proposed to solve the multidimensional vibrational Schroedinger equation in the model of non-interacting anharmonic oscillators via the expansion in hyperspherical harmonics.Comment: 11 pages, 2 figures, uses aipproc.sty. Presented at the Fifth Williamsburg Workshop on First-Principles Calculations for Ferroelectric

Ab initio Simulations of Fe-based Ferric Wheels

Based on first-principles density-functional theory calculations we investigate the electronic structure of hexanuclear "ferric wheels" M Fe_6[N(CH_2 CH_2 O)_3]_6 Cl (M = Li, Na) in their antiferromagnetic ground state. The electronic structure is presented in form of spin- and site-resolved local densities of states. The latter clearly indicate that the magnetic moment is distributed over several sites. The local moment at the iron site is still the largest one with about 4 mu_B, thus indicating the valence state of iron to be closer to Fe(II) than to commonly accepted Fe(III). The local spin of S=5/2 per iron site, following from magnetization measurements, is perfectly reproduced if one takes the moments on the neighbor atoms into account. The largest magnetic polarization is found on the apical oxygen atom, followed by nitrogen bridging oxygens. These findings are confirmed by a map of spatial spin density. A further goal of the present study has been a comparative test of two different DFT implementations, Siesta and NRLMOL. They yield a very good agreement down to small details in the electronic structure.Comment: 10 pages, 3 embedded postscript figures, to be published in Molecular Physics Reports (proceedings of the Summer School on New Magnetics - Bedlewo, Poland, September 2003). Two references update

Limits of structure stability of simple liquids revealed by study of relative fluctuations

We analyse the inverse reduced fluctuations (inverse ratio of relative volume fluctuation to its value in the hypothetical case where the substance acts an ideal gas for the same temperature-volume parameters) for simple liquids from experimental acoustic and thermophysical data along a coexistence line for both liquid and vapour phases. It has been determined that this quantity has a universal exponential character within the region close to the melting point. This behaviour satisfies the predictions of the mean-field (grand canonical ensemble) lattice fluid model and relates to the constant average structure of a fluid, i.e. redistribution of the free volume complementary to a number of vapour particles. The interconnection between experiment-based fluctuational parameters and self-diffusion characteristics is discussed. These results may suggest experimental methods for determination of self-diffusion and structural properties of real substances.Comment: 5 pages, 4 figure

Density functional simulation of small Fe nanoparticles

We calculate from first principles the electronic structure, relaxation and magnetic moments in small Fe particles, applying the numerical local orbitals method in combination with norm-conserving pseudopotentials. The accuracy of the method in describing elastic properties and magnetic phase diagrams is tested by comparing benchmark results for different phases of crystalline iron to those obtained by an all-electron method. Our calculations for the bipyramidal Fe_5 cluster qualitatively and quantitatively confirm previous plane-wave results that predicted a non-collinear magnetic structure. For larger bcc-related (Fe_35) and fcc-related (Fe_38, Fe_43, Fe_62) particles, a larger inward relaxation of outer shells has been found in all cases, accompanied by an increase of local magnetic moments on the surface to beyond 3 mu_B.Comment: 15 pages with 6 embedded postscript figures, updated version, submitted to Eur.Phys.J.