The reconstruction of Rh(001) upon oxygen adsorption

We report on a first-principles study of the structure of O/Rh(001) at half a monolayer of oxygen coverage, performed using density-functional theory. We find that oxygen atoms sit at the center of the black squares of a chess-board, $c(2\times 2)$, pattern. This structure is unstable against a rhomboid distortion of the black squares, which shortens the distance between an O atom and two of the four neighboring Rh atoms, while lengthening the distance with respect to the other two. We actually find that the surface energy is further lowered by allowing the O atom to get off the short diagonal of the rhombus so formed. We predict that the latter distortion is associated with an order-disorder transition, occurring below room temperature. The above rhomboid distortion of the square lattice may be seen as a rotation of the empty, white, squares. Our findings are at variance with recent claims based on STM images, according to which it is instead the black squares which would rotate. We argue that these images are indeed compatible with our predicted reconstruction pattern.Comment: 14 pages (inclusive of 5 figures). To appear on Surface Scienc

Interplay between Bonding and Magnetism in the Adsorption of NO on Rh Clusters

We have studied the adsorption of NO on small Rh clusters, containing one to five atoms, using density functional theory in both spin-polarized and non-spin-polarized forms. We find that NO bonds more strongly to Rh clusters than it does to Rh(100) or Rh(111); however, it also quenches the magnetism of the clusters. This (local) effect results in reducing the magnitude of the adsorption energy, and also washes out the clear size-dependent trend observed in the non-magnetic case. Our results illustrate the competition present between the tendencies to bond and to magnetize, in small clusters.Comment: Submitted to J. of Chem. Phy

Van der Waals Coefficients of Atoms and Molecules from a Simple Approximation for the Polarizability

A simple and computationally efficient scheme to calculate approximate imaginary-frequency dependent polarizability, hence asymptotic van der Waals coefficient, within density functional theory is proposed. The dynamical dipolar polarizabilities of atoms and molecules are calculated starting from the Thomas-Fermi-von Weizs\"acker (TFvW) approximation for the independent-electron kinetic energy functional. The van der Waals coefficients for a number of closed-shell ions and a few molecules are hence calculated and compared with available values obtained by fully first-principles calculations. The success in these test cases shows the potential of the proposed TFvW approximate response function in capturing the essence of long range correlations and may give useful information for constructing a functional which naturally includes van der Waals interactions.Comment: 6 pages, 4 figures. To appear in Phys. Rev.

Analysis of methane-to-methanol conversion on clean and defective Rh surfaces

We investigate by density-functional theory simulations several elementary reactions associated to direct methane-to-methanol conversion on clean Rh(111) surfaces and on Rh adatoms on Rh(111). Energy barriers and reaction paths have been determined by the nudged elastic band method. The rate-limiting step in the process, C-O bond formation, has higher activation energy than the one for complete methane dehydrogenation. Our analysis enables us to understand the effect of defects on the reactivity and rules out Rh as candidate catalyst for methanol synthesis

Efficient and accurate calculation of exact exchange and RPA correlation energies in the Adiabatic-Connection Fluctuation-Dissipation theory

Recently there has been a renewed interest in the calculation of exact-exchange and RPA correlation energies for realistic systems. These quantities are main ingredients of the so-called EXX/RPA+ scheme which has been shown to be a promising alternative approach to the standard LDA/GGA DFT for weakly bound systems where LDA and GGA perform poorly. In this paper, we present an efficient approach to compute the RPA correlation energy in the framework of the Adiabatic-Connection Fluctuation-Dissipation formalism. The method is based on the calculation of a relatively small number of eigenmodes of RPA dielectric matrix, efficiently computed by iterative density response calculations in the framework of Density Functional Perturbation Theory. We will also discuss a careful treatment of the integrable divergence in the exact-exchange energy calculation which alleviates the problem of its slow convergence with respect to Brillouin zone sampling. As an illustration of the method, we show the results of applications to bulk Si, Be dimer and atomic systems.Comment: 12 pages, 6 figures. To appear in Phys. Rev.

Ab-initio numerical studies in semiconductor alloys

This thesis is devoted to the theoretical study, by ab initio numerical methods, of the physical properties of substitutional semiconductor alloys. Nowadays, ab initio numerical methods allow to study quite accurately the physical properties of moderately complex periodic systems. These methods exploit the periodicity of the system, and can be applied to disordered systems (such as the substitutional semiconductor alloys), where the periodicity is lost, by replacing the original non-periodic system by a periodic one, which contains several unequivalent atoms in a large unit cell (supercell), distributed in such a way to reproduce the local atomic coordination present in the alloy. However, since this approximation is the better the larger the supercell used, an accurate description of disorder can require supercells so large (500 ÷ 1000 atoms) that the usual methods become too expensive and new techniques have to be developed. The chemical similarity between semiconductor components allows one to employ a perturbative approach in the study of their alloys. Exploiting the efficiency of modern perturbation techniques, we have been able to map the complex alloy problem onto much simpler models that, keeping the same accuracy of a complete first principles approach, can be easily studied with large supercells. By this approach, the structure, the thermodynamics, the lattice dynamics and the electronic structure of a few semiconductor alloys has been studied successfully