Materials Theory

We carry out a completely first-principles study of the ferroelectric phase transitions in BaTiO 3 . Our approach takes advantage of two features of these transitions: the structural changes are small, and only low-energy distortions are important. Based on these observations, we make systematically improvable approximations which enable the parameterization of the complicated energy surface. The parameters are determined from first-principles total-energy calculations using ultra-soft pseudopotentials and a preconditioned conjugate-gradient scheme. The resulting effective Hamiltonian is then solved by Monte Carlo simulation. The calculated phase sequence, transition temperatures, latent heats, and spontaneous polarizations are all in good agreement with experiment. We find the transitions to be intermediate between order-disorder and displacive character. We find all three phase transitions to be of first order. The roles of different interactions are discussed.

Following the approach of Yu, Singh, and Krakauer [Phys. Rev. B 43 (1991) 6411] we extended the linearized augmented plane wave code WIEN of Blaha, Schwarz, and coworkers by the evaluation of forces. In this paper we describe the approach, demonstrate the high accuracy of the force calculation, and use them for an efficient geometry optimization of poly-atomic systems.

Ab initio local-density-functional-theory calculations of formation energies, surface stress, and multilayer relaxations are reported for the (111), (100), and (110) surfaces of Rh. The study is performed using ultrasoft pseudopotentials and plane waves in a parallel implementation. Calculated values are in good agreement with previous studies where they exist. In particular, we confirm recent results on surface stress anisotropy of transition metals.

Motivated by recent experiments by Yuse and Sano (Nature, 362, 329 (1993)), we propose a discrete model of linear springs for studying fracture in thin and elastically isotropic brittle films. The method enables us to draw a map of the stresses in the material. Cracks generated by the model, imposing a moving thermal gradient in the material, can branch or wiggle depending on the driving parameters. The results may be used to compare with other recent theoretical work, or to design future experiments.

Using helium atom scattering Hulpke and L"udecke recently observed a giant phonon anomaly for the hydrogen covered W(110) and Mo(110) surfaces. An explanation which is able to account for this and other experiments is still lacking. Below we present density-functional theory calculations of the atomic and electronic structure of the clean and hydrogen-covered Mo(110) surfaces. For the full adsorbate monolayer the calculations provide evidence for a strong Fermi surface nesting instability. This explains the observed anomalies and resolves the apparent inconsistencies of different experiments.

The large interest in the properties of transition metal surfaces has been recently fostered by inelastic helium atom scattering experiments carried out by Hulpke and Luedecke. Sharp and giant anomalies in the surface phonon dispersion curves along Gamma-H and Gamma-S have been detected on W(110) and Mo(110) at a coverage of one monolayer of hydrogen. At the same critical wave vectors a smaller second indentation is present in the experimental phonon branches. Recently we have proposed a possible interpretation which is able to explain this and other experiments. In this paper we discuss results of our recent ab initio calculations of the atomic and electronic properties of the clean and H-covered Mo(110) surface in more details. For the full monolayer coverage the calculated Fermi-surface contours are characterized by strong nesting features which originate the observed anomalies.

The generalized stacking fault (GSF) energy surfaces have received considerable attention due to their close relation to the mechanical properties of solids. We present a detailed study of the GSF energy surfaces of silicon within the framework of density functional theory. We have calculated the GSF energy surfaces for the shuffle and glide set of the (111) plane, and that of the (100) plane of silicon, paying particular attention to the effects of the relaxation of atomic coordinates. Based on the calculated GSF energy surfaces and the Peierls-Nabarro model, we obtain estimates for the dislocation profiles, core energies, Peierls energies, and the corresponding stresses for various planar dislocations of silicon.

Among other things (e.g. steering and steric effects in dissociative adsorption) we had predicted that the initial sticking probability of H_2 molecules impinging at clean Pd(100) exhibits oscillations, reflecting the quantum nature of the scattering process. In the preceding comment Rettner and Auerbach (RA) analyze experimental results and conclude that these oscillations are not detectable and thus either not existing or at least very small. In this reply we argue that the experimental study of RA is not conclusive to rule out the existence of quantum oscillations in the scattering of H_2 and note several problems and incongruities in their study.

Using the non-empirical Variational Induced Breathing (VIB) model, the thermal properties of periclase (MgO) under high pressures and temperatures are investigated using molecular dynamics, which includes all anharmonic effects. Equations of state for temperatures up to 3000K and pressures up to 310 GPa were calculated. Bulk modulus, thermal expansivity, Anderson-Gruneisen parameter, thermal pressure, Gruneisen parameter and their pressure and temperature dependencies are studied in order to better understand high pressure effects on thermal properties. The results agree very well with experiments and show that the thermal expansivity decreases with pressure up to about 100 GPa ( η =0.73), and is almost pressure and temperature independent above this compression. It is also effected by anharmonicity at zero pressure and temperatures above 2500K. The thermal pressure changes very little with increasing pressures and temperatures, and the Gruneisen parameter is temperature independent and decreases slightly with pressure.

We performed high-dimensional quantum dynamical calculations of the dissociative adsorption and associative desorption of hydrogen on Cu(111). The potential energy surface (PES) is obtained from density functional theory calculations. Two regimes of dynamics are found, at low energies sticking is determined by the minimum energy barrier, at high energies by the distribution of barrier heights. Experimental results are well-reproduced qualitatively, but some quantitative discrepancies are identified as well.