First-Principles Calculation of Electric Field Gradients and Hyperfine Couplings in YBa2Cu3O7

The local electronic structure of YBa2Cu3O7 has been calculated using first-principles cluster methods. Several clusters embedded in an appropriate background potential have been investigated. The electric field gradients at the copper and oxygen sites are determined and compared to previous theoretical calculations and experiments. Spin polarized calculations with different spin multiplicities have enabled a detailed study of the spin density distribution to be made and a simultaneous determination of magnetic hyperfine coupling parameters. The contributions from on-site and transferred hyperfine fields have been disentangled with the conclusion that the transferred spin densities essentially are due to nearest neighbour copper ions only with marginal influence of ions further away. This implies that the variant temperature dependencies of the planar copper and oxygen NMR spin-lattice relaxation rates are only compatible with commensurate antiferromagnetic correlations. The theoretical hyperfine parameters are compared with those derived from experimental data.Comment: 14 pages, 12 figures, accepted to appear in EPJ

First principles study of local electronic and magnetic properties in pure and electron-doped Nd2_2CuO4_4

The local electronic structure of Nd2CuO4 is determined from ab-initio cluster calculations in the framework of density functional theory. Spin-polarized calculations with different multiplicities enable a detailed study of the charge and spin density distributions, using clusters that comprise up to 13 copper atoms in the CuO2plane. Electron doping is simulated by two different approaches and the resulting changes in the local charge distribution are studied in detail and compared to the corresponding changes in hole doped La2CuO4. The electric field gradient (EFG) at the copper nucleus is investigated in detail and good agreement is found with experimental values. In particular the drastic reduction of the main component of the EFG in the electron-doped material with respect to LaCuO4 is explained by a reduction of the occupancy of the 3d3z^2-r^2 atomic orbital. Furthermore, the chemical shieldings at the copper nucleus are determined and are compared to results obtained from NMR measurements. The magnetic hyperfine coupling constants are determined from the spin density distribution

Ground state properties of heavy alkali halides

We extend previous work on alkali halides by calculations for the heavy-atom species RbF, RbCl, LiBr, NaBr, KBr, RbBr, LiI, NaI, KI, and RbI. Relativistic effects are included by means of energy-consistent pseudopotentials, correlations are treated at the coupled-cluster level. A striking deficiency of the Hartree-Fock approach are lattice constants deviating by up to 7.5 % from experimental values which is reduced to a maximum error of 2.4 % by taking into account electron correlation. Besides, we provide ab-initio data for in-crystal polarizabilities and van der Waals coefficients.Comment: accepted by Phys. Rev.

THEORETICAL STUDIES OF BILIPROTEIN CHROMOPHORES AND RELATED BILE PIGMENTS BY MOLECULAR ORBITAL AND RAMACHANDRAN TYPE CALCULATIONS

Ramachandran calculations have been used to gain insight into steric hindrance in bile pigments related to biliprotein chromophores. The high optical activity of denatured phycocyanin, as compared to phycoerythrin, has been related to the asymmetric substitution at ring A, which shifts the equilibrium towards the P-helical form of the chromophore. Geometric effects on the electronic structures and transitions have then been studied by molecular orbital calculations for several conjugation systems including the chromophores of phycocyanin. phytochrome P,, cations, cation radicals and tautomeric forms. For these different chromophores some general trends can be deduced. For instance, for a given change in the gross shape (e.g. either unfolding of the molecule from a cyclic-helical to a fully extended geometry, or upon out-of-plane twists of the pyrrole ring A) of the molecules under study, the predicted absorption spectra all change in a simikar way. Nonetheless, there are characteristic distinctions between the different n-systems, both in the transition energies and the charge distribution, which can be related to their known differences in spectroscopic properties and their reactivity

Correlation effects in ionic crystals: I. The cohesive energy of MgO

High-level quantum-chemical calculations, using the coupled-cluster approach and extended one-particle basis sets, have been performed for (Mg2+)n (O2-)m clusters embedded in a Madelung potential. The results of these calculations are used for setting up an incremental expansion for the correlation energy of bulk MgO. This way, 96% of the experimental cohesive energy of the MgO crystal is recovered. It is shown that only 60% of the correlation contribution to the cohesive energy is of intra-ionic origin, the remaining part being caused by van der Waals-like inter-ionic excitations.Comment: LaTeX, 20 pages, no figure

Ground-state properties of rutile: electron-correlation effects

Electron-correlation effects on cohesive energy, lattice constant and bulk compressibility of rutile are calculated using an ab-initio scheme. A competition between the two groups of partially covalent Ti-O bonds is the reason that the correlation energy does not change linearly with deviations from the equilibrium geometry, but is dominated by quadratic terms instead. As a consequence, the Hartree-Fock lattice constants are close to the experimental ones, while the compressibility is strongly renormalized by electronic correlations.Comment: 1 figure to appear in Phys. Rev.