First-principles study of the electronic structure and dynamical electronic excitations of strong spin-orbit metal Pb: bulk, surface and nanosized films

En la presente tesis se ha realizado el estudio de primeros principios (esto es, sinhacer uso de parámetros ajustables) de la estructura electrónica y la dinámica deexcitaciones electrónicas en plomo, tanto en volumen como en superficie y en formade películas de espesor nanométrico. Al presentar el plomo un número atómico alto(82), deben tenerse en cuenta los efectos relativistas. Con este fin, el doctorando haimplementado el acoplo espín-órbita en los códigos computacionales que hanrepresentado la principal herramienta de trabajo.En volumen, se han encontrado fuertes efectos relativistas asi como de lalocalización de los electrones, tanto en la respuesta dieléctrica (excitacioneselectrónicas colectivas) como en el tiempo de vida de electrones excitados. Lacomparación de nuestros resultados con medidas experimentales ha ayudado aprofundizar en dichos efectos.En el estudio de las películas a escala nanométrica se han hallado fuertes efectoscuánticos debido al confinamiento de los estados electrónicos. Dichos efectos semanifiestan tanto en el estado fundamental (en acuerdo con estudiosexperimentales), como en la respuesta dieléctrica a través de la aparición y dinámicade plasmones de diversas características. Los efectos relativistas, a pesar de no serimportantes en la estructura electrónica de las películas, son los responsables de ladesaparación del plasmón de baja energía en nuestros resultados.

Electronic structure and phonon thermodynamics of iron alloys

Inelastic neutron scattering (INS) and nuclear-resonant inelastic x-ray scattering (NRIXS) were used to measure phonon spectra of FeV as a B2- ordered compound and as a bcc solid solution. Contrary to the behavior of ordering alloys studied to date, the phonons in the B2-ordered phase are softer than in the solid solution. Ordering increases the vibrational entropy, which stabilizes the ordered phase to higher temperatures. Ab initio calculations show that the number of electronic states at the Fermi level increases upon ordering, enhancing the screening between ions, and reducing the interatomic force constants. The effect of screening is larger at the V atomic sites than at the Fe atomic sites.

The phonon spectra of Au-rich alloys of fcc Au-Fe were also measured. The main effect on the vibrational entropy of alloying comes from a stiffening of the Au partial phonon density of states (DOS) with Fe concentration that increases the miscibility gap temperature. The magnitude of the effect is non- linear and it is reduced at higher Fe concentrations. Force constants were calculated for several compositions and show a local stiffening of Au–Au bonds close to Fe atoms, but Au–Au bonds that are farther away do not show this effect. Phonon DOS curves calculated from the force constants reproduced the experimental trends. The Au–Fe bond is soft and favors ordering, but a charge transfer from the Fe to the Au atoms stiffens the Au–Au bonds enough to favor unmixing. The stiffening is attributed to two main effects comparable in magnitude: an increase in electron density in the free-electron-like states, and stronger sd-hybridization.

INS and NRIXS measurements were performed at elevated temperatures on B2-ordered FeTi and NRIXS measurements were performed at high pressures. The high-pressure behavior is quasi- harmonic. The softening of the phonon DOS curves with temperature is strongly nonharmonic. Calculations of the force constants and Born-von Karman fits to the experimental data show that the bonds between second nearest neighbors (2nn) are much stiffer than those between 1nn, but fits to the high temperature data show that the former softens at a faster rate with temperature. The Fe–Fe bond softens more than the Ti–Ti bond. The unusual stiffness of the 2nn bond is explained by the calculated charge distribution, which is highly aspherical and localized preferentially in the t2g orbitals. Ab initio molecular dynamics (AIMD) simulations show a charge transfer from the t2g orbitals to the eg orbitals at elevated temperatures. The asphericity decreases linearly with temperature and is more severe at the Fe sites.

First-principles study of the electronic structures and absorption spectra for the PbMoO4 crystal with lead vacancy

The electronic structures and absorption spectra for the perfect PbMoO4 crystal and the crystal containing lead vacancy V-Pb(2-) with lattice structure optimized are calculated using density functional theory code CASTEP. The calculated absorption spectra of the PbMoO4 crystal containing V-Pb(2-) exhibit three absorption bands peaking at 2.0 eV (620 nm), 3.0 eV (413 run) and 3.3 eV (375 nm), which are in good agreement with experimental values. The theory predicts that the 390 nm, 430 nm and 580 run absorption bands are related to the existence of V-Pb(2-) in the PbMoO4 crystal.

First-principles calculations of electronic structures and absorption spectra of YAlO3 crystals with F center

National Nature Science Foundation of China (Grant No. 60607015)