arXiv subjects
Publications and source records attributed to Emilio Artacho.
Based on bond arguments, a Hamiltonian is introduced to describe the fundamental physics of the collective rotations of oxygen atoms in oxides. Values for the relevant material parameters are estimated for silica and Cu oxides. Zero-temperature phase diagrams are presented; the different phases and associated transitions are characterized. Phases with non-phononic excitations are found.
The problem of the low-energy highly-anharmonic quantum dynamics of isolated impurities in solids is addressed by using path-integral Monte Carlo simulations. Interstitial oxygen in silicon is studied as a prototypical example showing such a behavior. The assignment of a "geometry" to the defect is discussed. Depending on the potential (or on the impurity mass), there is a "classical" regime, where the maximum probability-density for the oxygen nucleus is at the potential minimum. There is another regime, associated to highly anharmonic potentials, where this is not the case. Both regimes are separated by a sharp transition. Also, the decoupling of the many-nuclei problem into a one-body Hamiltonian to describe the low-energy dynamics is studied. The adiabatic potential obtained from the relaxation of all the other degrees of freedom at each value of the coordinate associated to the low-energy motion, gives the best approximation to the full many-nuclei problem.
We present a method to perform fully selfconsistent density-functional calculations, which scales linearly with the system size and which is well suited for very large systems. It uses strictly localized pseudoatomic orbitals as basis functions. The sparse Hamiltonian and overlap matrices are calculated with an $O(N)$ effort. The long range selfconsistent potential and its matrix elements are computed in a real-space grid. The other matrix elements are directly calculated and tabulated as a function of the interatomic distances. The computation of the total energy and atomic forces is also done in $O(N)$ operations using truncated, Wannier-like localized functions to describe the occupied states, and a band-energy functional which is iteratively minimized with no orthogonality constraints. We illustrate the method with several examples, including carbon and silicon supercells with up to 1000 Si atoms and supercells of $β$-C$_3$N$_4$. We apply the method to solve the existing controversy about the faceting of large icosahedral fullerenes by performing dynamical simulations on C$_{60}$, C$_{240}$, and C$_{540}$.
The interstitial oxygen centers in silicon and germanium are reconsidered and compared in an analysis based on the first-principles total-energy determination of the potential-energy surface of the centers, and a calculation of their respective low energy excitations and infrared absorption spectra. The total-energy calculations reveal unambiguously that interstitial oxygen is quantum delocalized, the delocalization being essentially different in silicon and in germanium. Oxygen in silicon lies at the bond center site in a highly anharmonic potential well, whereas in germanium it is found to rotate almost freely around the original Ge-Ge bond it breaks. This different delocalization is the origin of the important differences in the low energy excitation spectra: there is a clear decoupling in rotation and vibration excitations in germanium, giving different energy scales (1 cm$^{-1}$ for the rotation, 200 cm$^{-1}$ for the $ν_2$ mode), whereas both motions are non-trivially mixed in silicon, in a common energy scale of around 30 cm$^{-1}$. The calculation of the vibrational spectra of the defect reveals the existence of vibrational modes (related to the $ν_1$ mode) never been experimentally observed due to their weak infrared activity. It is found that the combination of these modes with the well established $ν_3$ asymmetric stretching ones is the origin of the experimentally well characterized modes at frequencies above the $ν_3$ mode frequency.
A method is presented to obtain {\it ab initio} upper and lower bounds to surface energies of stress-driven discommensurate surface structures, possibly non-periodic or exhibiting very large unit cells. The instability of the stressed, commensurate parent of the discommensurate structure sets an upper bound to its surface energy; a lower bound is defined by the surface energy of an ideally commensurate but laterally strained hypothetical surface system. The surface energies of the phases of the Si(111):Ga and Ge(111):Ga systems and the energies of the discommensurations are determined within $\pm 0.2$ eV.
The projection of the eigenfunctions obtained in standard plane-wave first-principle calculations is used for analyzing atomic-orbital basis sets. The "spilling" defining the error in such a projection allows the evaluation of the quality of an atomic-orbital basis set for a given system and its systematic variational optimization. The same projection allows obtaining the band structure and the Hamiltonian matrix elements in the previously optimized atomic basis. The spilling is shown to correlate with the mean square error in the energy bands, indicating that the basis optimization via spilling minimization is qualitatively equivalent to the energy-minimization scheme, but involves a much smaller computational effort. The spilling minimization also allows the optimization of bases for uses different than total-energy calculations, like the description of the band gap in semiconductors. The method is applied to the characterization of finite-range pseudo-atomic orbitals {[}O. F. Sankey and D. J. Niklewski, Phys. Rev. B {\bf 40}, 3979 (1989){]} in comparison to infinite-range pseudo-atomic and Slater-type orbitals. The bases are evaluated and optimized for several zincblende semiconductors and for aluminum. The quality of the finite-range orbitals is found to be perfectly comparable to the others with the advantage of a limited range of interacions. A simple scheme is proposed to expand the basis without increasing the range. It is found that a double-$z$ basis substantially improves the basis performance on diamond, whereas $d$-polarization is required for Si and Al for similar results. Finally, the projection allows the chemical analysis of the plane-wave results via population analysis on the previously optimized atomic basis.
The projection of the eigenfunctions obtained in standard plane-wave first-principle electronic-structure calculations into atomic-orbital basis sets is proposed as a formal and practical link between the methods based on plane waves and the ones based on atomic orbitals. Given a candidate atomic basis, ({\it i}) its quality is evaluated by its projection into the plane-wave eigenfunctions, ({\it ii}) it is optimized by maximizing that projection, ({\it iii}) the associated tight-binding Hamiltonian and energy bands are obtained, and ({\it iv}) population analysis is performed in a natural way. The proposed method replaces the traditional trial-and-error procedures of finding appropriate atomic bases and the fitting of bands to obtain tight-binding Hamiltonians. Test calculations of some zincblende semiconductors are presented.
The problem of the geometry of interstitial oxygen in silicon is settled by proper consideration of the quantum delocalization of the oxygen atom around the bond-center position. The calculated infrared absorption spectrum accounts for the 517 and 1136 cm$^{-1}$ bands in their position, character, and isotope shifts. The asymmetric lineshape of the 517 cm$^{-1}$ peak is also well reproduced. A new, non-infrared-active, symmetric-stretching mode is found at 596 cm$^{-1}$. First-principles calculations are presented supporting the nontrivial quantum delocalization of the oxygen atom.