Electron correlation effects in boron clusters BnQ (for Q=-1,0, 1 and n ≤13) based on quantum Monte Carlo simulations

We present all-electron quantum Monte Carlo simulations on the anionic, neutral, and cationic boron clusters BnQ with up to 13 atoms (Q=-1,0,+1 and n≤ 13). Accurate total energies of these...

Структура электронных состояний соединений Gd-=SUB=-5-=/SUB=-Sb-=SUB=-3-=/SUB=- и Gd-=SUB=-5-=/SUB=-Ge-=SUB=-2-=/SUB=-Sb по данным зонных расчетов и оптической спектроскопии

Results of investigations of the electronic structure and optical properties of Gd5Sb3 and Gd5Ge2Sb compounds are presented. Calculations of band spectra were carried out in frame of local density approximation with a correction for strong correlation effects in 4f shell of rare-earth ion (DFT+U+SO method). Optical constants of these materials were measured by ellipsometric technique in wide wavelength interval. Energy dependencies of a number of spectral parameters were determined. The nature of quantum light absorption is discussed on the base of comparative analysis of the experimental and calculated spectra of optical conductivity.

HYPERFINE STRUCTURE PARAMETERS FOR COMPLEX ATOMS WITHIN RELATIVISTIC MANY-BODY PERTURBATION THEORY

The calculational results for the hyperfine structure (HFS) parameters for the Mn atom (levels of the configuration 3d64s) and the results of advanced calculating the HFS constants and nuclear quadrupole moment for the radium isotope are obtained on the basis of computing within the relativistic many-body perturbation theory formalism with a correct and effective taking into account the exchange-correlation, relativistic, nuclear and radiative corrections. Analysis of the data shows that an account of the interelectron correlation effects is crucial in the calculation of the hyperfine structure parameters. The fundamental reason of physically reasonable agreement between theory and experiment is connected with the correct taking into account the inter-electron correlation effects, nuclear (due to the finite size of a nucleus), relativistic and radiative corrections. The key difference between the results of the relativistic Hartree-Fock Dirac-Fock and many-body perturbation theory methods calculations is explained by using the different schemes of taking into account the inter-electron correlations as well as nuclear and radiative ones.

Orbital selectivity in the normal state of KFe(2)Se(2) superconductor

Using density functional dynamical mean-field theory, we show how correlation effects lead to pseudogap and Kondo-quasiparticle features in the electronic structure of pure and doped KFe2Se2 superconductor. Therein, correlation- and doping-induced orbital differentiation are linked to the emergence of an incoherent-coherent crossover in the normal state of KFe2Se2 superconductor. This crossover explains the puzzling temperature and doping dependent evolution of resistivity and Hall coefficient, seen in experiments of alkali-metal intercalated iron-selenide superconductors. Our microscopic description emphasises the role of incoherent and coherent electronic excitations towards unconventional transport responses of strange, bad-metals.

Correlation Effects in Trimeric Acylphloroglucinols

Trimeric acylphloroglucinols (T-ACPLs) are a subclass of the large class of acylphloroglucinols—derivatives of 1,3,5-trihydroxybenzene containing an R–C=O group. T-ACPL molecules contain three acylphloroglucinol moieties linked by methylene bridges. Many of them are present in natural sources and exhibit biological activities, often better than the corresponding activities of monomeric acylphloroglucinols. All the stable conformers of T-ACPLs contain seven intramolecular hydrogen bonds, which constitute the dominant stabilising factors. A total of 38 different T-ACPLs, including both naturally occurring and model molecules, have been calculated at the HF and DFT/B3LYP levels. The DFT/B3LYP calculations were carried out both without and with Grimme’s dispersion correction, to highlight the dispersion (and, therefore, also electron correlation) effects for these molecules. The roles of dispersion are evaluated considering the effects of Grimme’s correction on the estimation of the conformers’ energies, the description of the characteristics of the individual hydrogen bonds, the conformers’ geometries and other molecular properties. Overall, the results offer a comprehensive overview of the conformational preferences of T-ACPL molecules, their intramolecular hydrogen bond patterns, and the correlation effects on their properties.

How the cation size impacts on the relaxational and diffusional dynamics of supercooled butylammonium-based ionic liquids: DPEBA–TFSI versus BTMA–TFSI

Li-bis(trifluoromethylsulfonyl)imide based ionic liquids with either butyl-trimethylammonium or N,N-dimethyl-N-(2-(propionyloxy)-ethyl)butan-1-ammonium as the anion were studied using proton and fluorine relaxometry as well as using field-gradient diffusometry to gain separate access to cation and anion dynamics in these compounds. The transport parameters obtained for these ionic liquids are compared with the estimates based on the conductivity data from literature and from the present work. The impact of cation size on correlation effects, the latter parameterized in terms of various Haven ratios, is mapped out.