Extending Hirshfeld-I to bulk and periodic materials

In this work, a method is described to extend the iterative Hirshfeld-I method, generally used for molecules, to periodic systems. The implementation makes use of precalculated pseudo-potential based charge density distributions, and it is shown that high quality results are obtained for both molecules and solids, such as ceria, diamond, and graphite. The use of such grids makes the implementation independent of the solid state or quantum chemical code used for studying the system. The extension described here allows for easy calculation of atomic charges and charge transfer in periodic and bulk systems.Comment: 11 pages, 4 Tables, 5 Figures, pre-referee draft only, much extended post referee version only available at publishe

Reply to 'Comment on "Extending Hirshfeld-I to bulk and periodic materials" '

The issues raised in the comment by T.A. Manz are addressed through the presentation of calculated atomic charges for NaF, NaCl, MgO, SrTiO$_3$ and La$_2$Ce$_2$O$_7$, using our previously presented method for calculating Hirshfeld-I charges in Solids [J. Comput. Chem.. doi: 10.1002/jcc.23088]. It is shown that the use of pseudo-valence charges is sufficient to retrieve the full all-electron Hirshfeld-I charges to good accuracy. Furthermore, we present timing results of different systems, containing up to over $200$ atoms, underlining the relatively low cost for large systems. A number of theoretical issues is formulated, pointing out mainly that care must be taken when deriving new atoms in molecules methods based on "expectations" for atomic charges.Comment: 7 pages, 2 Tables, 2 figure

Continuous-feed nanocasting process for the synthesis of bismuth nanowire composites

We present a novel, continuous-feed nanocasting procedure for the synthesis of bismuth nanowire structures embedded in the pores of a mesoporous silica template. The immobilization of a bismuth salt inside the silica template from a diluted metal salt solution yields a sufficiently high loading to obtain electrically conducting bulk nanowire composite samples after reduction and sintering the nanocomposite powders. Electrical resistivity measurements of sintered bismuth nanowires embedded in the silica template reveal size-quantization effects

Z-Pencils

The matrix pencil (A,B) = {tB-A | t \in C} is considered under the assumptions that A is entrywise nonnegative and B-A is a nonsingular M-matrix. As t varies in [0,1], the Z-matrices tB-A are partitioned into the sets L_s introduced by Fiedler and Markham. As no combinatorial structure of B is assumed here, this partition generalizes some of their work where B=I. Based on the union of the directed graphs of A and B, the combinatorial structure of nonnegative eigenvectors associated with the largest eigenvalue of (A,B) in [0,1) is considered.Comment: 8 pages, LaTe

Tuning of CeO2_2 buffer layers for coated superconductors through doping

The appearance of microcracks in CeO$_2$ buffer layers, as used in buffer layer architectures for coated superconductors, indicates the presence of stress between this buffer layer and the substrate. This stress can originate from the differences in thermal expansion or differences in lattice parameters between the CeO$_2$ buffer layer and the substrate. In this article, we study, by means of \textit{ab initio} density functional theory calculations, the influence of group IV doping elements on the lattice parameter and bulk modulus of CeO$_2$. Vegard's law behavior is found for the lattice parameter in systems without oxygen vacancies, and the Shannon crystal radii for the doping elements are retrieved from the lattice expansions. We show that the lattice parameter of the doped CeO$_2$ can be matched to that of the La$_2$Zr$_2$O$_7$ coated NiW substrate substrate for dopant concentrations of about $5\%$, and that bulk modulus matching is either not possible or would require extreme doping concentrations.Comment: 5 pages, 1 table, 2 figures, EMRS 2011 Fall meeting symposium on Stress, structure and stoichiometry effects on nanomaterial

Eigenvalues of matrices with tree graphs

AbstractWhen the undirected graph of a real square matrix is a tree of forest, we establish finitely computable tests yielding information about the magnitudes and multiplicities to the eigenvalues of the matrix. Applying these tests to system designs expressed as signed directed graphs can be sufficient to guarantee controllability of the associated linear dynamical systems

Some remarks on matrix stability with application to Turing instability

AbstractAn example of a 4×4 matrix is given that provides a counterexample to a result on Turing (diffusion-driven) instability and also answers negatively a conjecture on strong stability. Such instability is shown to arise from nonreal eigenvalues. The relevance and the connection of our example to classes of matrix stability known in the literature are discussed