Density functional and dynamics study of the dissociative adsorption of hydrogen on

a b s t r a c t A first principles study is performed to investigate the adsorption characteristics of hydrogen on magnesium surface. Substitutional and on-surface adsorption energies are calculated for Mg (0 0 0 1) surface alloyed with the selected elements. To further analyze the hydrogen-magnesium interaction, first principles molecular dynamics method is used which simulates the behavior of H 2 at the surface. Also, charge density differences of substitutionally doped surface configurations were illustrated. Accordingly, Mo and Ni are among the elements yielding lower adsorption energies, which are found to be À9.2626 and À5.2995 eV for substitutionally alloyed surfaces, respectively. In light of the dynamic calculations, Co as an alloying element is found to have a splitting effect on H 2 in 50 fs, where the first hydrogen atom is taken inside the Mg substrate right after the decomposition and the other after 1300 fs. An interesting remark is that, elements which acquire higher chances of adsorption are also seen to be competent at dissociating the hydrogen molecule. Furthermore, charge density distributions support the results of molecular dynamics simulations, by verifying the distinguished effects of most of the 3d and 4d transition metals

Cation- and vacancy-ordering in Li_xCoO_2

Using a combination of first-principles total energies, a cluster expansion technique, and Monte Carlo simulations, we have studied the Li/Co ordering in LiCoO_2 and Li-vacancy/Co ordering in CoO_2. We find: (i) A ground state search of the space of substitutional cation configurations yields the (layered) CuPt structure as the lowest-energy state in the octahedral system LiCoO_2 (and CoO_2), in agreement with the experimentally observed phase. (ii) Finite temperature calculations predict that the solid-state order- disorder transitions for LiCoO_2 and CoO_2 occur at temperatures (~5100 K and ~4400 K, respectively) much higher than melting, thus making these transitions experimentally inaccessible. (iii) The energy of the reaction E(LiCoO_2) - E(CoO_2) - E(Li) gives the average battery voltage V of a Li_xCoO_2/Li cell. Searching the space of configurations for large average voltages, we find that CuPt (a monolayer superlattice) has a high voltage (V=3.78 V), but that this could be increased by cation randomization (V=3.99 V), partial disordering (V=3.86 V), or by forming a 2-layer Li_2Co_2O_4 superlattice along (V=4.90 V).Comment: 12 Pages, RevTeX galley format, 5 figures embedded using epsf Phys. Rev. B (in press, 1998

Low thermal conductivity of the layered oxide (Na,Ca)Co_2O_4: Another example of a phonon glass and an electron crystal

The thermal conductivity of polycrystalline samples of (Na,Ca)Co_2O_4 is found to be unusually low, 20 mW/cmK at 280 K. On the assumption of the Wiedemann-Franz law, the lattice thermal conductivity is estimated to be 18 mW/cmK at 280 K, and it does not change appreciably with the substitution of Ca for Na. A quantitative analysis has revealed that the phonon mean free path is comparable with the lattice parameters, where the point-defect scattering plays an important role. Electronically the same samples show a metallic conduction down to 4.2 K, which strongly suggests that NaCo_2O_4 exhibits a glass-like poor thermal conduction together with a metal-like good electrical conduction. The present study further suggests that a strongly correlated system with layered structure can act as a material of a phonon glass and an electron crystal.Comment: 5 pages 3 figures, to be published in Phys. Rev.