First-principles periodic calculation of four-body spin terms in high-Tc cuprate superconductors

A general mapping between the energy of pertinent magnetic solutions and the diagonal terms of the spin Hamiltonian in a local representation provides the first general framework to extract accurate values for the many body terms of extended spin Hamiltonians from periodic first-principle calculations. Estimates of these terms for La2CuO4, the paradigm of high-Tc superconductor parent compounds, and for the SrCu2O3 ladder compound are reported. For La2CuO4, present results support experimental evidence by Toader et al. [Phys. Rev. Lett. 94, 197202 (2005)]. For SrCu2O3 even larger four-body spin amplitudes are found together with Jl/Jr=1 and non-negligible ferromagnetic interladder exchange.

First-principles periodic calculation of four-body spin terms in high-Tc Cuprate superconductors

A general mapping between the energy of pertinent magnetic solutions and the diagonal terms of the spin Hamiltonian in a local representation provides the first general framework to extract accurate values for the many body terms of extended spin Hamiltonians from periodic first-principle calculations. Estimates of these terms for La2CuO4, the paradigm of high-Tc superconductor parent compounds, and for the SrCu2O3 ladder compound are reported. For La2CuO4, present results support experimental evidence by Toader et al. [Phys. Rev. Lett. 94, 197202 (2005)]. For SrCu2O3 even larger four-body spin amplitudes are found together with Jl/Jr=1 and non-negligible ferromagnetic interladder exchange.

Towards and ab initio description of magnetism in ionic solids

The physical contributions to the KNiF3 magnetic exchange coupling integral have been obtained from specially designed ab initio cluster model calculations. Three important mechanisms have been identified. These are the delocalization of the magnetic orbitals into the anion p band, the variational contribution of the second-order interactions, and the many-body terms hidden in the two-body operator and the Heisenberg Hamiltonian.

Electronic structure and properties of AlN

The electronic structure of the wurtzite-type phase of aluminum nitride has been investigated by means of periodic ab initio Hartree-Fock calculations. The binding energy, lattice parameters (a,c), and the internal coordinate (u) have been calculated. All structural parameters are in excellent agreement with the experimental data. The electronic structure and bonding in AlN are analyzed by means of density-of-states projections and electron-density maps. The calculated values of the bulk modulus, its pressure derivative, the optical-phonon frequencies at the center of the Brillouin zone, and the full set of elastic constants are in good agreement with the experimental data.

Extent and limitations of density functional theory in describing magnetic systems

The performance of density-functional theory to solve the exact, nonrelativistic, many-electron problem for magnetic systems has been explored in a new implementation imposing space and spin symmetry constraints, as in ab initio wave function theory. Calculations on selected systems representative of organic diradicals, molecular magnets and antiferromagnetic solids carried out with and without these constraints lead to contradictory results, which provide numerical illustration on this usually obviated problem. It is concluded that the present exchange-correlation functionals provide reasonable numerical results although for the wrong physical reasons, thus evidencing the need for continued search for more accurate expressions.

Electronic structure and properties of Cu2O

The structural and electronic properties of Cu2O have been investigated using the periodic Hartree-Fock method and a posteriori density-functional corrections. The lattice parameter, bulk modulus, and elastic constants have been calculated. The electronic structure of and bonding in Cu2O are analyzed and compared with x-ray photoelectron spectroscopy spectra, showing a good agreement for the valence-band states. To check the quality of the calculated electron density, static structure factors and Compton profiles have been calculated, showing a good agreement with the available experimental data. The effective electron and hole masses have been evaluated for Cu2O at the center of the Brillouin zone. The calculated interaction energy between the two interpenetrated frameworks in the cuprite structure is estimated to be around -6.0 kcal/mol per Cu2O formula. The bonding between the two independent frameworks has been analyzed using a bimolecular model and the results indicate an important role of d10-d10 type interactions between copper atoms.

Absence of collective effects in Heisenberg systems with localized magnetic moments

Existence of collective effects in magnetic coupling in ionic solids is studied by mapping spin eigenstates of the Heisenberg and exact nonrelativistic Hamiltonians on cluster models representing KNiF3, K2NiF4, NiO, and La2CuO4. Ab initio techniques are used to estimate the Heisenberg constant J. For clusters with two magnetic centers, the values obtained are about the same for models having more magnetic centers. The absence of collective effects in J strongly suggests that magnetic interactions in this kind of ionic solids are genuinely local and entangle only the two magnetic centers involved.

Magnetic coupling in the weac ferromagnet CuF2

CuF2 is known to be an antiferromagnetic compound with a weak ferromagnetism due to the anisotropy of its monoclinic unit cell (Dzialoshinsky-Moriya mechanism). We investigate the magnetic ordering of this compound by means of ab initio periodic unrestricted Hartree-Fock calculations and by cluster calculations which employ state-of-the-art configuration interaction expansions and modern density functional theory techniques. The combined use of periodic and cluster models permits us to firmly establish that the antiferromagnetic order arises from the coupling of one-dimensional subunits which themselves exhibit a very small ferromagnetic coupling between Cu neighbor cations. This magnetic order could be anticipated from the close correspondence between CuF2 and rutile crystal structures.

Ab Initio study of magnetic interactions in the KCuF3 and K2CuF4 low-dimensional Systems

The ab initio cluster model approach has been used to study the electronic structure and magnetic coupling of KCuF3 and K2CuF4 in their various ordered polytype crystal forms. Due to a cooperative Jahn-Teller distortion these systems exhibit strong anisotropies. In particular, the magnetic properties strongly differ from those of isomorphic compounds. Hence, KCuF3 is a quasi-one-dimensional (1D) nearest neighbor Heisenberg antiferromagnet whereas K2CuF4 is the only ferromagnet among the K2MF4 series of compounds (M=Mn, Fe, Co, Ni, and Cu) behaving all as quasi-2D nearest neighbor Heisenberg systems. Different ab initio techniques are used to explore the magnetic coupling in these systems. All methods, including unrestricted Hartree-Fock, are able to explain the magnetic ordering. However, quantitative agreement with experiment is reached only when using a state-of-the-art configuration interaction approach. Finally, an analysis of the dependence of the magnetic coupling constant with respect to distortion parameters is presented.