Electron-phonon relaxation and excited electron distribution in zinc oxide and anatase

We propose a first-principle method for evaluations of the time-dependent electron distribution function of excited electrons in the conduction band of semiconductors. The method takes into account the excitations of electrons by external source and the relaxation to the bottom of conduction band via electron-phonon coupling. The methods permits calculations of the non-equilibrium electron distribution function, the quasi-stationary distribution function with steady-in-time source of light, the time of setting of the quasi-stationary distribution and the time of energy loss via relaxation to the bottom of conduction band. The actual calculations have been performed for titanium dioxide in the anatase structure and zinc oxide in the wurtzite structure. We find that the quasi-stationary electron distribution function for ZnO is a fermi-like curve that rises linearly with increasing excitation energy whereas the analogous curve for anatase consists of a main peak and a shoulder. The calculations demonstrate that the relaxation of excited electrons and the setting of the quasi-stationary distribution occur within the time no more than 500 fsec for ZnO and 100 fsec for anatase. We also discuss the applicability of the effective phonon model with energy-independent electron-phonon transition probability. We find that the model only reproduces the trends in changing of the characteristic times whereas the precision of such calculations is not high. The rate of energy transfer to phonons at the quasi-stationary electron distribution also have been evaluated and the effect of this transfer on the photocatalyses has been discussed. We found that for ZnO this rate is about 5 times less than in anatase.Comment: 21 p., 9 figure

Linear-response theory and lattice dynamics: a muffin-tin orbital approach

A detailed description of a method for calculating static linear-response functions in the problem of lattice dynamics is presented. The method is based on density functional theory and it uses linear muffin-tin orbitals as a basis for representing first-order corrections to the one-electron wave functions. As an application we calculate phonon dispersions in Si and NbC and find good agreement with experiments.Comment: 18 pages, Revtex, 2 ps figures, uuencoded, gzip'ed, tar'ed fil

Electronic and structural properties of superconducting MgB2_2, CaSi2_2 and related compounds

We report a detailed study of the electronic and structural properties of the 39K superconductor \mgbtwo and of several related systems of the same family, namely \mgalbtwo, \bebtwo, \casitwo and \cabesi. Our calculations, which include zone-center phonon frequencies and transport properties, are performed within the local density approximation to the density functional theory, using the full-potential linearized augmented plane wave (FLAPW) and the norm-conserving pseudopotential methods. Our results indicate essentially three-dimensional properties for these compounds; however, strongly two-dimensional $\sigma$-bonding bands contribute significantly at the Fermi level. Similarities and differences between \mgbtwo and \bebtwo (whose superconducting properties have not been yet investigated) are analyzed in detail. Our calculations for \mgalbtwo show that metal substitution cannot be fully described in a rigid band model. \casitwo is studied as a function of pressure, and Be substitution in the Si planes leads to a stable compound similar in many aspects to diborides.Comment: Revised version, Phys.Rev.B in pres

Lattice instabilities of cubic NiTi from first principles

The phonon dispersion relation of NiTi in the simple cubic B2 structure is computed using first-principles density-functional perturbation theory with pseudopotentials and a plane-wave basis set. Lattice instabilities are observed to occur across nearly the entire Brillouin zone, excluding three interpenetrating tubes of stability along the (001) directions and small spheres of stability centered at R. The strongest instability is that of the doubly degenerate M5' mode. The atomic displacements of one of the eigenvectors of this mode generate a good approximation to the observed B19' ground-state structure.Comment: 11 pages, 3 figure

Optical studies of gap, hopping energies and the Anderson-Hubbard parameter in the zigzag-chain compound SrCuO2

We have investigated the electronic structure of the zigzag ladder (chain) compound SrCuO2 combining polarized optical absorption, reflection, photoreflectance and pseudo-dielectric function measurements with the model calculations. These measurements yield an energy gap of 1.42 eV (1.77 eV) at 300 K along (perpendicular) to the Cu-O chains. We have found that the lowest energy gap, the correlation gap, is temperature independent. The electronic structure of this oxide is calculated using both the local-spin-density-approximation with gradient correction method, and the tight-binding theory for the correlated electrons. The calculated density of electronic states for non-correlated and correlated electrons shows quasi-one-dimensional character. The correlation gap values of 1.42 eV (indirect transition) and 1.88 eV (direct transition) have been calculated with the electron hopping parameters t = 0.30 eV (along a chain), t_yz = 0.12 eV (between chains) and the Anderson-Hubbard repulsion on copper sites U= 2.0 eV. We concluded that SrCuO_2 belongs to the correlated-gap insulators.Comment: 24 pages, 8 figures, to be published in Phys.Rev.

Phonons and related properties of extended systems from density-functional perturbation theory

This article reviews the current status of lattice-dynamical calculations in crystals, using density-functional perturbation theory, with emphasis on the plane-wave pseudo-potential method. Several specialized topics are treated, including the implementation for metals, the calculation of the response to macroscopic electric fields and their relevance to long wave-length vibrations in polar materials, the response to strain deformations, and higher-order responses. The success of this methodology is demonstrated with a number of applications existing in the literature.Comment: 52 pages, 14 figures, submitted to Review of Modern Physic

Accurate ab initio spin densities

We present an approach for the calculation of spin density distributions for molecules that require very large active spaces for a qualitatively correct description of their electronic structure. Our approach is based on the density-matrix renormalization group (DMRG) algorithm to calculate the spin density matrix elements as basic quantity for the spatially resolved spin density distribution. The spin density matrix elements are directly determined from the second-quantized elementary operators optimized by the DMRG algorithm. As an analytic convergence criterion for the spin density distribution, we employ our recently developed sampling-reconstruction scheme [J. Chem. Phys. 2011, 134, 224101] to build an accurate complete-active-space configuration-interaction (CASCI) wave function from the optimized matrix product states. The spin density matrix elements can then also be determined as an expectation value employing the reconstructed wave function expansion. Furthermore, the explicit reconstruction of a CASCI-type wave function provides insights into chemically interesting features of the molecule under study such as the distribution of $\alpha$- and $\beta$-electrons in terms of Slater determinants, CI coefficients, and natural orbitals. The methodology is applied to an iron nitrosyl complex which we have identified as a challenging system for standard approaches [J. Chem. Theory Comput. 2011, 7, 2740].Comment: 37 pages, 13 figure

Electronic Structure Calculation by First Principles for Strongly Correlated Electron Systems

Recent trends of ab initio studies and progress in methodologies for electronic structure calculations of strongly correlated electron systems are discussed. The interest for developing efficient methods is motivated by recent discoveries and characterizations of strongly correlated electron materials and by requirements for understanding mechanisms of intriguing phenomena beyond a single-particle picture. A three-stage scheme is developed as renormalized multi-scale solvers (RMS) utilizing the hierarchical electronic structure in the energy space. It provides us with an ab initio downfolding of the global band structure into low-energy effective models followed by low-energy solvers for the models. The RMS method is illustrated with examples of several materials. In particular, we overview cases such as dynamics of semiconductors, transition metals and its compounds including iron-based superconductors and perovskite oxides, as well as organic conductors of kappa-ET type.Comment: 44 pages including 38 figures, to appear in J. Phys. Soc. Jpn. as an invited review pape

Antisymmetric Magnetic Interactions in Oxo-Bridged Copper(II) Bimetallic Systems

The antisymmetric magnetic interaction is studied using correlated wave-function-based calculations in oxo-bridged copper bimetallic complexes. All of the anisotropic multispin Hamiltonian parameters are extracted using spin-orbit state interaction and effective Hamiltonian theory. It is shown that the methodology is accurate enough to calculate the antisymmetric terms, while the small symmetric anisotropic interactions require more sophisticated calculations. The origin of the antisymmetric anisotropy is analyzed, and the effect of geometrical deformations is addressed.

Physics Opportunities with the 12 GeV Upgrade at Jefferson Lab

This white paper summarizes the scientific opportunities for utilization of the upgraded 12 GeV Continuous Electron Beam Accelerator Facility (CEBAF) and associated experimental equipment at Jefferson Lab. It is based on the 52 proposals recommended for approval by the Jefferson Lab Program Advisory Committee.The upgraded facility will enable a new experimental program with substantial discovery potential to address important topics in nuclear, hadronic, and electroweak physics.Comment: 64 page