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We study the scaling behavior of the characteristic length of precursor magnetic nanostructures above the Curie temperature with the correlation length of quenched-in disorder. We found that the modulation length of the nanostructures $\ensuremath{\xi}$ follows the scaling law $\ensuremath{\xi}\ensuremath{\sim}\sqrt{\overline{D}}$, where $\overline{D}$ is the average size of the magnetized regions in the material. The scaling behavior of the average size of these regions, $\overline{D}$, with the correlation length of the disorder, $\ensuremath{\sigma}$, depends on the properties of the disorder. For Gaussian disorder, we find that $\overline{D}$ scales with the disorder correlation length as $\overline{D}\ensuremath{\sim}{\ensuremath{\sigma}}^{a∕2}$, where $a$ is the exponent of the leading term of the pair correlation function of the disorder in the limit $r\ensuremath{\rightarrow}0$, $\ensuremath{\Gamma}(r)\ensuremath{\approx}\ensuremath{\epsilon}[1\ensuremath{-}(1∕a){(r∕\ensuremath{\sigma})}^{a}]$. These results are quite general and applicable to other systems, e.g., ferroelectric precursors, independent of the nature of the long-range dipolar forces.

The electronic structure and properties of cerium oxides (CeO2 and Ce2O3) have been studied in the framework of the LDA+U and GGA(PW91)+U implementations of density functional theory. The dependence of selected observables of these materials on the effective U parameter has been investigated in detail. The examined properties include lattice constants, bulk moduli, density of states, and formation energies of CeO2 and Ce2O3. For CeO2, the LDA+U results are in better agreement with experiment than the GGA+U results whereas for the computationally more demanding Ce2O3 both approaches give comparable accuracy. Furthermore, as expected, Ce2O3 is much more sensitive to the choice of the U value. Generally, the PW91 functional provides an optimal agreement with experiment at lower U energies than LDA does. In order to achieve a balanced description of both kinds of materials, and also of nonstoichiometric CeO2¿x phases, an appropriate choice of U is suggested for LDA+U and GGA+U schemes. Nevertheless, an optimum value appears to be property dependent, especially for Ce2O3. Optimum U values are found to be, in general, larger than values determined previously in a self-consistent way.

6 pages.-- PACS numbers: 73.21.-b, 73.22.-f, 71.15.Mb.-- Final full-text version of the paper available at: http://dx.doi.org/10.1103/PhysRevB.76.245302., Within density functional theory, we address the effect of an in-plane electric field [script E] on the ground state and the density dipole response of a many-electron quantum ring, which is also submitted to a perpendicular magnetic field B. Addition energies and density dipole spectra are discussed as a function of [script E]. For the two-electron case, an exact numerical calculation is performed, obtaining the spin-phase diagram in the [script E]-B plane and showing that transitions between singlet and triplet spin states can be induced by varying the fields. We also find that, in spite of the deformation that [script E] causes in the electronic density, the spin of the ground state of a given electron number ring is very robust, changing little as the strength of the electric field is reasonably increased., This work has been performed under Grants No. FIS2005-01414 and No. FIS2005-02796 from DGI (Spain), No. 2005SGR00343 from Generalitat de Catalunya, and Grant No. INFN07-30 from the Italian INFN-Spanish DGI agreement.

The computational approach to the Hirshfeld [Theor. Chim. Acta 44, 129 (1977)] atom in a molecule is critically investigated, and several difficulties are highlighted. It is shown that these difficulties are mitigated by an alternative, iterative version, of the Hirshfeld partitioning procedure. The iterative scheme ensures that the Hirshfeld definition represents a mathematically proper information entropy, allows the Hirshfeld approach to be used for charged molecules, eliminates arbitrariness in the choice of the promolecule, and increases the magnitudes of the charges. The resulting Hirshfeld-I charges correlate well with electrostatic potential derived atomic charges

A consistent extension of local spin density approximation (LSDA) to account for mass and dielectric mismatches in nanocrystals is presented. The extension accounting for variable effective mass is exact. Illustrative comparisons with available configuration interaction calculations show that the approach is also very reliable when it comes to account for dielectric mismatches. The modified LSDA is as fast and computationally low demanding as LSDA. Therefore, it is a tool suitable to study large particle systems in inhomogeneous media without much effort.

En el presente trabajo se emplean pseudopotenciales empíricos locales para estudiar la estructura electrónica de aluminio y silicio con el fin de obtener un procedimiento unificado, pero a la vez sencillo, para describir diferentes tipos de materiales. También se muestra que para casos reales la teoría de perturbaciones a primer orden falla para describir el ancho de la banda de energía prohibida. Una descripción más adecuada requiere del empleo de términos de segundo y tercer orden. La influencia del radio de corte (que es un parámetro libre en la teoría de pseudopotenciales) es estudiada en detalle. Efectos de presión y dilatación sobre el material también son discutidos. In the present work we employ local empirical pseudopotentials to study the electronic structure of aluminium and silicon searching for an unified but also simple procedure to describe different kind of materials. It is also shown that for real cases first order perturbation theory is not enough to explain the width of the energy gap. A more realistic description requires higher orders. The influence of the cut-off radius (the free parameter in the pseudopotential theory) is also studied in detail. Effects of pressure and dilatation are also discussed. Revisión por pares

Within local-spin-density functional theory, we have investigated the `dissociation' of few-electron circular vertical semiconductor double quantum ring artificial molecules at zero magnetic field as a function of inter-ring distance. In a first step, the molecules are constituted by two identical quantum rings. When the rings are quantum mechanically strongly coupled, the electronic states are substantially delocalized, and the addition energy spectra of the artificial molecule resemble those of a single quantum ring in the few-electron limit. When the rings are quantum mechanically weakly coupled, the electronic states in the molecule are substantially localized in one ring or the other, although the rings can be electrostatically coupled. The effect of a slight mismatch introduced in the molecules from nominally identical quantum wells, or from changes in the inner radius of the constituent rings, induces localization by offsetting the energy levels in the quantum rings. This plays a crucial role in the appearance of the addition spectra as a function of coupling strength particularly in the weak coupling limit., 18 pages, 8 figures, submitted to Physical Review B

The atomic and electronic structure, formation energy, and the energy barriers for migration have been calculated for the neutral O vacancy point defect F center in cubic SrTiO3 employing various implementations of density functional theory DFT. Both bulk and TiO2-terminated 001 surface F centers have been considered. Supercells of different shapes containing up to 320 atoms have been employed. The limit of an isolated single oxygen vacancy in the bulk corresponds to a 270-atom supercell, in contrast to commonly used supercells containing 40–80 atoms. Calculations carried out with the hybrid B3PW functional show that the F center level approaches the conduction band bottom to within 0.5 eV, as the supercell size increases up to 320 atoms. The analysis of the electronic density maps indicates, however, that this remains a small-radius center with the two electrons left by the missing O ion being redistributed mainly between the vacancy and the 3d z2 atomic orbitals of the two nearest Ti ions. As for the dynamical properties, the calculated migration energy barrier in the low oxygen depletion regime is predicted to be 0.4 eV. In contrast, the surface F center exhibits a more delocalized character, which leads to significantly reduced ionization and migration energies. Results obtained are compared with available experimental data.

10 pages, 13 figures, 3 tables., Differential scanning calorimetry experiments have been performed under magnetic field in RCo2 Laves phases compounds (R=Pr, Nd, Tb, Dy, Ho, and Er). The thermodynamical nature of the ferromagnetic transitions in PrCo2 and NdCo2 is clarified, after the controversy present in the literature about the character of their ordering transitions. The magnetocaloric effect in the compounds showing a first-order magnetostructural transition (R=Dy, Ho, and Er)is characterized. The latent heat, L, and the entropy change at the transition, S, have been studied by inducing the transition sweeping the temperature at a constant field and sweeping the field at a constant temperature. Results from calorimetric data show that L is essentially temperature independent, suggesting that the first order transitions in RCo2 are dominated by the structural effects. The magnetocaloric effect has been also characterized from magnetization data and the results are in excellent agreement with those from calorimetric data. However, the corresponding values of S for isothermal and isofield experiments differsignificantly. We interpret the differences in terms of the broadness of the transitions and prove that the various S values reported in literature for first-order transitions are not always directly comparable., This work has been partially funded by the Fundación Areces, the Spanish CICYT research Projects Nos. MAT2002-04178-C04-03, MAT2005-002454, and MAT2003-01124, the FEDER program, the Aragonese CAMRADS research group, and the Catalan DURSI research Project No. 2001SGR00066.We thank N. Plugaru and M. J. Pastor for sample preparation, Ll. Mañosa, A. Planes, and L. Morellón for fruitful discussions, J. Rodríguez and J. Sánchez-Marcos for their magnetization facilities at the Universidad de Cantabria, and J. Bartolomé for a critical reading of the manuscript. J.H. acknowledges MEC for the Ph.D. grant.

Selected configuration interaction (SCI) for atomic and molecular electronic structure calculations is reformulated in a general framework encompassing all CI methods. The linked cluster expansion is used as an intermediate device to approximate CI coefficients B(K) of disconnected configurations (those that can be expressed as products of combinations of singly and doubly excited ones) in terms of CI coefficients of lower-excited configurations where each K is a linear combination of configuration-state-functions (CSFs) over all degenerate elements of K. Disconnected configurations up to sextuply excited ones are selected by Brown's energy formula, Delta E(K) = (E-H(KK))B(K)2/(1-B(K)2), with B(K) determined from coefficients of singly and doubly excited configurations. The truncation energy error from disconnected configurations, Delta E(dis), is approximated by the sum of Delta E(K)s of all discarded Ks. The remaining (connected) configurations are selected by thresholds based on natural orbital concepts. Given a model CI space M, a usual upper bound E(S) is computed by CI in a selected space S, and E(M) = E(S) + Delta E(dis) + delta E, where delta E is a residual error which can be calculated by well-defined sensitivity analyses. An SCI calculation on Ne ground state featuring 1077 orbitals is presented. Convergence to within near spectroscopic accuracy (0.5 cm(-1)) is achieved in a model space M of 1.4 x 10(9) CSFs (1.1 x 10(12) determinants) containing up to quadruply excited CSFs. Accurate energy contributions of quintuples and sextuples in a model space of 6.5 x 10(12) CSFs are obtained. The impact of SCI on various orbital methods is discussed. Since Delta E(dis) can readily be calculated for very large basis sets without the need of a CI calculation, it can be used to estimate the orbital basis incompleteness error. A method for precise and efficient evaluation of E(S) is taken up in a companion paper.

Els objectius d'aquest treball són donar una perspectiva general de la metodologia de les mesures continues de forma, que permeten una descripció senzilla, però acurada, de l'entorn de coordinació en compostos de metalls de transició. S'introduirà una nova eina associada a la metodologia de les mesures de forma pel seguiment d'estructures que es troben en camins d'interconversió entre poliedres. Les mesures de forma seran emprades per analitzar 1'esteroquímica de compostos organometàl·lics, comparant aquests compostos i els seus lligands típics amb els anàlegs de química de coordinació. S'estudiarà l'estereoquímica de compostos tetracoordinats i pentacoordinats en funció de la configuració electrònica del metall i de les restriccions estereoquímiques imposades per lligands amb diferent denticitat. Pels compostos tetracoordinats, es farà un estudi de les corbes d'energia per totes les configuracions electròniques i pels diferents estats de spin, per correlacionar la distribució de les estructures experimentals amb les geometries i estats de spin predits a nivell teòric. Es mostrarà com es poden obtenir un conjunt de regles senzilles per la predicció de l'entom de coordinació en compostos tetracoordinats en funció de l'estructura electrònica del metall, i quins són els factors que poden modificar l'estat de spin del metall. Finalment, i donada la relació intima que hi ha entre estructura i propietats, es farà un estudi de la correlació entre el paràmetre de desdoblarnent a camp zero, calculat teòricament, i l'entom de coordinació del metall.

Se presenta la capacidad de las técnicas de modelización molecular basadas en métodos de la química cuántica para predecir la estructura molecular y electrónica de polímeros conductores. Concretamente, se discute la aplicabilidad de estas herramientas computacionales al estudio de diferentes aspectos del politiofeno y sus derivados: geometría molecular y planaridad, cambios estructurales producidos por el dopado, propiedades electrónicas y desarrollo de nuevos materiales conductores.

Se presenta la capacidad de las técnicas de modelización molecular basadas en métodos de la química cuántica para predecir la estructura molecular y electrónica de polímeros conductores. Concretamente, se discute la aplicabilidad de estas herramientas computacionales al estudio de diferentes aspectos del politiofeno y sus derivados: geometría molecular y planaridad, cambios estructurales producidos por el dopado, propiedades electrónicas y desarrollo de nuevos materiales conductores. The ability of molecular modeling techniques based on quantum chemical methods to predict the molecular and electronic structure of organic conducting polymers is examined. More specifically, we report on the applicability of these computational tools to study different aspects of polythiophene and its derivatives: molecular geometry and planarity, the structural changes induced by the doping process, the electronic properties and the design of new conducting materials.

A systematic study of the bulk and surface geometrical and electronic properties of a series of transition-metal carbides (TMC with TM = Ti, V, Zr, Nb, Mo, Hf, Ta, and W) by first-principles methods is presented. It is shown that in these materials the chemical bonding is strongly covalent, the cohesive energies being directly related to the bonding-antibonding gap although the shift of the center of the C(2s) band related peak in the density of states with respect to diamond indicates that some metal to carbon charge transfer does also take place. The (001) face of these metal carbides exhibits a noticeable surface rumpling which grows along the series. It is shown that neglecting surface relaxation results in very large errors on the surface energy and work function. The surface formation induces a significant shift of electronic energy levels with respect to the corresponding values in the bulk. The extent and nature of the shift can be understood from simple bonding-antibonding arguments and is enhanced by the structural rippling of this surface.

The theoretic study of electronic structure parameters in transition metal compounds is interesting in solid state chemistry. Many of these parameters are related with magnetism. The magnetic properties of these materials, in particular those of the transition metal oxides, are the basis of a possible technological interest since, for example, some of these doped compounds could be superconductors or feature large magnetorresistences. Because of the important role of these materials, many theoretic works study the electronic structure of transition metal compounds using simple models. Besides the parameters related to magnetism, quantum chemistry can also provide detailed information about spectroscopic parameters. Anderson proposed in the 50's the first theoretic interpretation for the behaviour of magnetic materials. In the next years qualitative interpretations were proposed to explain magnetism. Perturbation theory was applied by de Loth et al. in the 80's to perform detailed analyses on the physical contributions to magnetic couplings showing that dynamical electron correlation in quantum mechanical calculations is crucial to reproduce the order of magnitude of couplings. Taking as a reference point that of de Loth, the DDCI method (Difference Dedicated Configuration Interaction) was developed. This is a selected configuration interaction technique where the configurations responsible for the physical effects are included. Our group satisfactorily utilised and developed this method to obtain accurate energy differences between electronic states.We herein used that method for the theoretical study of magnetic coupling constants, J, and to get other electronic structure parameters in a series of transition metal oxides. We have also used perturbative methods such as the CASPT2, cheaper than the DDCI, which allows dealing with larger systems. The main conclusions that arose from this work are:1. Although the DDCI method with minimal CAS performs correctly in the study of magnetic couplings, it is expensive and other possibilities should be taken into account, namely, the CI procedure including an extended CAS adding the orbital with ligand character and its monoexcitations. This space assures including the polarisation of the charge distribution in the wave function, in response to the charge transfer from ligand to metal (LMCT).2. The extended active space must include the LMCT effects. The results show that the projection of a model vector with pure bridging ligand character in the set of inactive orbitals results in an effective scheme to account for all important LMCT configurations in the reference wave function.3. Using this scheme in the spin ladder compounds, one observes an overestimation of the antiferromagnetic component of J, which can be partially overcame including the 2h, 2p and 1h-2p excitations with the DDCI2 method. 4. Due to the particular structure of the spin ladders, there are many different interactions between copper ions. For the magnetic coupling, the second neighbouring interaction is very small, so it has not to be taken into account in the study of the macroscopic properties. The interactions along the Cu-O-Cu bonding are important in the SrCu2O3 and Sr2Cu3O5 compounds, whereas the distorted planes in CaCu2O3 reduce the rung interaction. We can observe the same weak interactions in the interladder. For this reason it is better to consider the CaCu2O3 compound as a 1D spin chain.5. We have applied the effective Hamiltonian technique using three different procedures to calculate the direct exchange parameter, Kab, the hopping integral, t, and the on site repulsion, U. The three procedures are: the Bloch Hamiltonian, the intermediate effective Hamiltonian and the Gram-Schmidt ortogonalisation. We suggest using the latter. Although it might be difficult to identify the high-energy states, this does not influence much this procedure and the negative values obtained for Kab vanish when IDDCI functions are used.6. We have studied the local d-d excitations in the 3d shell of the manganese ion of CaMnO3. We have obtained the d-d excitation energies and the ligand field energy at CASSCF and CASPT2 level. We observed a reduction of the 10Dq parameter when going from the small [MnO6] to the large [MnO6Al6Ca8O16] clusters.7. In the CaMnO3 perovskite there are no states with predominant CT character below 4.5 eV with the [MnO6] cluster, although using the [MnO6Al6Ca8O16] cluster this value is also reduced by 1 eV.8. For the ground state, a d3 excited state or a CT state of CaMnO3, the formal charge of manganese ion remains +3., El estudio teórico de los parámetros de estructura electrónica en materiales de metales de transición es un campo emergente en química y física del estado sólido. Muchos de estos parámetros están relacionados con fenómenos magnéticos. Las propiedades magnéticas de estos materiales, en particular de los óxidos de metales de transición, son la base de un posible interés tecnológico ya que, por ejemplo, algunos de estos materiales dopados, pueden llegar a ser superconductores y en otros se observan magnetoresistencias muy grandes. Debido a la importancia de estos materiales muchos trabajos teóricos tratan de estudiar la compleja estructura electrónica de estos compuestos de metales de transición utilizando necesariamente modelos simplificados. Nuevos avances en química cuántica hacen que sea posible un tratamiento ab initio de la estructura electrónica de dichos materiales. Aparte de las propiedades magnéticas, la química cuántica también puede dar información detallada sobre parámetros relacionados con la espectroscopia. Se ha utilizado como punto de partida para el estudio teórico del magnetismo el modelo de Anderson que en los años 50 propuso la primera interpretación teórica al comportamiento magnético de los materiales. En años posteriores se propusieron interpretaciones qualitativas para explicar el comportamiento magnético. Ya en los años 80, de Loth et al. utilizaron la Teoría de Perturbaciones para realizar un análisis detallado de las contribuciones físicas que contribuyen al acoplamiento magnético y demostraron que la inclusión de la correlación dinámica es crucial para reproducir el orden de magnitud del acoplamiento. Más tarde, teniendo como punto de partida el método de de Loth et al. se desarrolló el método DDCI (Difference Dedicated Configuration Interaction). Este es un método de interacción de configuraciones seleccionada donde se incluyeron las configuraciones responsables de los efectos físicos que contribuyen de forma significativa a la descripción física del acoplamiento. Este método ha sido desarrollado y utilizado por nuestro grupo dando resultados satisfactorios para las diferencias de energía entre diferentes estados electrónicos. En este trabajo se ha usado este método para el estudio teórico de la constante de acoplamiento magnético, J, así como para extraer otros parámetros de estructura electrónica en una serie de óxidos de metales de transición. También se han utilizado métodos perturbativos como el CASPT2, menos costoso que el mencionado DDCI, y que, por tanto, permite tratar sistemas con un número elevado de átomos o que dan lugar a espacios modelos grandes. Las principales conclusiones del trabajo presentado son:1. Los resultados obtenidos en este trabajo corroboran que se obtienen estimaciones correctas de las constantes de acoplamiento magnético y otros parámetros de estructura electrónica con el método DDCI partiendo de un espacio activo mínimo. No obstante, el coste computacional del método DDCI, sugiere la necesidad de una estrategia alternativa, como sería el procedimiento de interacción de configuraciones que incluye un CAS extendido añadiendo el orbital con fuerte caràcter del ligando y sus monoexcitaciones. Este espacio asegura la inclusión en la función de onda de la polarización de la distribución de carga en respuesta a la transferencia de carga del ligando hacia el metal (LMCT). 2. El espacio activo extendido debe asegurar que incluya de forma óptima los efectos LMCT. Se han comparado diferentes procedimientos para obtener el espacio activo extendido y los resultados muestran que la proyección de un vector modelo con carácter puro del ligando puente en el conjunto de orbitales inactivos resulta un esquema efectivo para introducir todas las configuraciones importantes LMCT en la función de onda de referencia.3. En los spin ladders este tratamiento reproduce peor los valores y tiende a sobrestimar la componente antiferromagnética del acoplamiento. Esta sobrestimación se remedia parcialmente añadiendo las excitaciones 2h y 2p a la expansión IC de acuerdo con el esquema DDCI2. La función de onda contiene así efectos de correlación dinámica de los electrones del ligando puente. Esto tiende a reducir la importancia de las excitaciones LMCT. Además, la función de onda incluye las excitaciones del tipo 1h-2p, las cuales contribuyen ferromagnéticamente al acoplamiento en los sistemas expuestos.4. La particular estructura de los spin ladders da lugar a un gran número de interacciones diferentes entre los centros de cobre. Para el acoplamiento magnético la interacción a segundos vecinos es muy pequeña, justificando que se desprecie en estudios de propiedades macroscópicas. En cambio sí que se tiene que tener en cuenta la interacción interladder. Las interacciones a lo largo de los enlaces Cu-O-Cu son importantes en los compuestos con Sr (SrCu2O3 y Sr2Cu3O5) mientras que la distorsión de los planos en el compuesto de Ca (CaCu2O3) reduce considerablemente la interacción a lo largo de los rungs. También se observa una débil interacción en el interladder. Este hecho hace que se entienda mejor el compuesto CaCu2O3 si se considera como una cadena unidimensional de espín.5. El cálculo del intercambio directo Kab, de la integral de salto t y la autorrepulsión efectiva en un centro U, se ha realizado utilizando técnicas de Hamiltonianos efectivos empleando tres prodecimientos distintos: Hamiltoniano de Bloch, Hamiltoniano hermítico mediante ortogonalización de Gram-Schmidt y Hamiltoniano efectivo intermedio. De los tres, se sugiere la utilización de la ortogonalización de Gram-Schmidt. El difícil reconocimiento de los estados altos en energía no repercute tanto en este procedimiento y los valores negativos que se obtienen de Kab desaparecen cuando se usan funciones IDDCI. 6. Se han estudiado las excitaciones locales dentro de la capa 3d del ion manganeso en la perovskita CaMnO3 obteniéndose los valores de las energías de las excitaciones d-d y la energía del campo cristalino a dos niveles de cálculo distintos CASSCF y CASPT2. Se observa una disminución del parámetro 10Dq en 1 eV cuando se pasa de tratar el material con el cluster [MnO6] al cluster [MnO6Al6Ca8O16].7. En la perovskita CaMnO3 no se encuentran estados con carácter predominante de transferencia de carga por debajo de los 4.5 eV con el cluster [MnO6], aunque utilizando el cluster [MnO6Al6Ca8O16], este valor también se reduce en 1 eV.8. En el compuesto CaMnO3, tanto para el estado fundamental como para un estado excitado d3 o un estado de transferencia de carga, la carga formal del ion manganeso se mantiene igual a +3.

In this work, the aromatic fluctuation index (FLU) that describes the fluctuation of electronic charge between adjacent atoms in a given ring is introduced as a new aromaticity measure. This new electronic criterion of aromaticity is based on the fact that aromaticity is related to the cyclic delocalized circulation of pi electrons. It is defined not only considering the amount of electron sharing between contiguous atoms, which should be substantial in aromatic molecules, but also taking into account the similarity of electron sharing between adjacent atoms. For a series of rings in 15 planar polycyclic aromatic hydrocarbons, we have found that, in general, FLU is strongly correlated with other widely used indicators of local aromaticity, such as the harmonic-oscillator model of aromaticity, the nucleus independent chemical shift, and the para-delocalization index (PDI). In contrast to PDI, the FLU index can be applied to study the aromaticity of rings with any number of members and it can be used to analyze both the local and global aromatic character of rings and molecules.

The energy associated with bosonic and fermionic pairs of topological spin defects in doped antiferromagnetic quantum spin-1/2 square lattice is estimated within a resonating valence bond scenario, as described by a t-t'-J-like model Hamiltonian, plus a t-perpendicular, responsible of a three-dimensional screening of the electrostatic repulsion within the bosonic pairs. For parameters appropriate for monolayered high-T_c superconductors, both fermionic and bosonic pairs show x^2-y^2 symmetry. We find a critical value of doping such that the energy of the bosonic pairs goes below twice the energy of two fermionic pairs at their Fermi level. This finding could be related to the onset of high-T_c superconductivity., Comment: 10 pages, 6 figures. To be published in Phys. Rev. B

The observation of coherent tunnelling in Cu2+ - and Ag2+ -doped MgO and CaO:Cu2+ was a crucial discovery in the realm of the Jahn-Teller (JT) effect. The main reasons favoring this dynamic behavior are now clarified through ab initio calculations on Cu2+ - and Ag2+ -doped cubic oxides. Small JT distortions and an unexpected low anharmonicity of the eg JT mode are behind energy barriers smaller than 25 cm-1 derived through CASPT2 calculations for Cu2+ - and Ag2+ -doped MgO and CaO:Cu2+ . The low anharmonicity is shown to come from a strong vibrational coupling of MO610- units (M=Cu,Ag) to the host lattice. The average distance between the d9 impurity and ligands is found to vary significantly on passing from MgO to SrO following to a good extent the lattice parameter.

Both the intermolecular interaction energies and the geometries for $M\ensuremath{\cdots}$ thiophene, $M\ensuremath{\cdots}$ pyrrole, ${M}^{n+}\ensuremath{\cdots}$ thiophene, and ${M}^{n+}\ensuremath{\cdots}$ pyrrole (with $M=\mathrm{Li}$, Na, K, Ca, and Mg; and ${M}^{n+}={\mathrm{Li}}^{+},\phantom{\rule{0.3em}{0ex}}{\mathrm{Na}}^{+},\phantom{\rule{0.3em}{0ex}}{\mathrm{K}}^{+},\phantom{\rule{0.3em}{0ex}}{\mathrm{Ca}}^{2+}$, and ${\mathrm{Mg}}^{2+}$) have been estimated using four commonly used density functional theory (DFT) methods: B3LYP, B3PW91, PBE, and MPW1PW91. Results have been compared to those provided by HF, MP2, and MP4 conventional ab initio methods. The PBE and MPW1PW91 are the only DFT methods able to provide a reasonable description of the $M\ensuremath{\cdots}\ensuremath{\pi}$ complexes. Regarding ${M}^{n+}\ensuremath{\cdots}\ensuremath{\pi}$ complexes, the four DFT methods have been proven to be adequate in the prediction of these electrostatically stabilized systems, even though they tend to overestimate the interaction energies.

The electronic structure and spectroscopic features of the optical spectra of oxygen vacancies in the bulk and on the 0001 surface of -Al2O3 have been studied by first-principles methods. The effect of oxygen vacancies on the crystalline structure has been determined by the appropriate atomic structure optimization carried out using a periodic model and density functional theory DFT calculations. Both, neutral F center and charged F+ center oxygen vacancies have been considered. Optical transitions arising from the excitations of the electron s trapped in the F+ and F centers, both on the surface and in the bulk of the material, have been studied using a suitable embedded cluster model approach. The cluster geometry, including the relaxation around the vacancy, has been taken from the periodic calculations. The transition energies and intensities have been obtained by applying the explicitly correlated multiconfigurational second-order perturbation theory method and also time-dependent DFT approaches. The present results are in good agreement with available experimental data for the bulk and provide a guide to interpret forthcoming experiments involving the spectroscopy of oxygen vacancies present in irradiated or defective -Al2O3 0001 surfaces.

La síntesis y el estudio de complejos polinucleares de metales de transición constituyen un área de gran interés en la Química Inorgánica. La presencia de varios centros metálicos en una misma molécula puede modificar la reactividad que cabría esperar en compuestos metálicos. Por otra parte, estos sistemas polinucleares sirven como modelos a escala molecular para el estudio de ciertos procesos catalíticos como los que tienen lugar sobre superficies metálicas u óxidos metálicos.El estudio teórico de dos familias de compuestos metálicos bien diferenciadas constituye el núcleo de esta tesis. En ambos casos el objetivo principal es ayudar a racionalizar las características químicas de las especies analizadas. El tratamiento se basará en cálculos teóricos mediante la teoría del funcional de la densidad, que han demostrado ser apropiados a la hora de estudiar agregados metálicos. Una primera parte, consta del estudio de la nueva familia de compuestos cubánicos de titanio que han sido recientemente sintetizados por el grupo del profesor Mena de la universidad de Alcalá de Henares. Un estudio teórico de dichos compuestos en colaboración conjunta con el trabajo en el laboratorio se ha venido realizando. Fruto de esta colaboración, nuevas pautas de investigación se han tratado de proponer por ambas partes. Como ejemplo, el análisis teórico para la obtención de espectros de resonancia magnética nuclear por métodos ab initio, que se expone en el segundo capitulo de la tesis, es fruto de un esfuerzo por parte de nuestro grupo por entender y racionalizar los datos de RMN obtenidos en el laboratorio para la caracterización de los compuestos. Además, fruto de los excelentes resultados obtenidos en este estudio, los conocimientos han sido aplicados a otros campos de interés dentro del grupo. Un estudio de la viabilidad para el análisis teórico del espectro de los núcleos de 183W en compuestos de Keggin forma un apartado importante en esta memoria.Fruto de una estancia de seis meses en el grupo del doctor McGrady de la universidad de York surge un segundo apartado basado en el estudio de las importantes capacidades catalizadoras de los compuestos binucleares de molibdeno con azufres puente. La gran importancia industrial de procesos de hidrogenación catalizados por este tipo de compuestos ha despertado un gran interés, no obstante algunos aspectos del mecanismo de estas reacciones permanecen sin aclarar. El estudio teórico de esta reacciones puede proporcionar un poco de luz a estos aspectos. Dentro del estudio de los compuestos cubánicos de titanio, los resultados principales se refieren a los asuntos siguientes:- Descripción de las características estructurales y electrónicas de las especies implicadas. La disposición de los ligandos tridentados, (precubanos) de fórmula general [{TiCp*(-O)}3(3-CR)] y [{TiCp*}(-NH)}3(3-N)], para actuar como ligandos macrocíclicos donores de seis-electrones proporciona una ruta eficaz para la obtención de estructuras cúbicas con esqueleto [MTi3(3-Y)(-X)3]. Reacción del ligando con el fragmento metálico Es de esperar que fragmentos de casi todos los grupos metálicos sean capaces de interactuar con estos ligandos. Así se ha estudiado la formación de estructuras cubánicas a partir de fragmentos metálicos de los grupos 1,2, 4-6, 9, 13 y 14. Cambios en la naturaleza de la interacción, en el comportamiento del ligando, estructura molecular han sido analizados. Los resultados muestran las versatilidad de estos ligandos para actuar no sólo como donores de electrones si no también como posibles aceptores a través de los orbitales vacíos de los metales. Una mención especial en este apartado es necesaria para los isomeros acetilénicos y vilidénicos encontrados a partir de la deprotonación del compuesto [{TiCp*(-O)}3(3-CMe)] por la interacción con fragmentos metálicos del grupo 2. En este caso, el núcleo formado por los átomos de titanio sirve como base para la estabilización de estas especies.- Estudio de la estabilidad de los compuestos y de los procesos energéticos en que están implicados (energías de la reacción, procesos de la isomerización). Un estudio de las condiciones experimentales que conducen a la obtención de estructuras cúbicas será analizado. El desplazamiento de ligandos lábiles en fragmentos metálicos por parte de los ligandos tridentados para formar los correspondientes cubanos ha sido probado, o también la activación de los enlaces nitrógeno-protón del ligando por interacción con el fragmento metálico. Estos procesos vienen caracterizados por unas condiciones energéticas favorables, estas condiciones son analizadas y estudiadas por su utilidad a la hora de proponer nuevas vías de síntesis en el laboratorio. Además, algunos compuestos presentarán evidencias del tener más que un isómero, o de experimentar un comportamiento dinámico en solución. Estas situaciones también se han descrito. Como resultado ha sido descrito el comportamiento de estas estructuras como ligandos mono- di- y tridentados, y adicionalmente como ligandos neutros o aniónicos. A su vez, respecto de la interacción con el fragmento metálico, un comportamiento como ligandos simples, que solo estabilizan el metal, o dobles, estabilizando metal y su respectivo contraión, han sido descritos.- La influencia del solvente también se ha evaluado debido a la importancia que tiene su presencia en la obtención o no de ciertos compuestos. La termoquímica relacionada con la presencia del disolvente ha sido analizada desde el punto de vista teórico, debido a la imposibilidad de explicar ciertos procesos a partir de estudios en fase gas. Un modelo basado en un medio continuo de constante dieléctrica conocida se utiliza para demostrar los efectos del solvente. Para una misma familia de compuestos, solamente en algunos casos la interacción con los ligandos precubánicos conducen a la formación de los correspondientes cubanos, o en condiciones muy específicas. Por ejemplo, ha sido estudiado que los efectos del solvente son un factor decisivo en la obtención de los cubanos a partir de las sales de metales alcalinos y alcalino térreos. Este efecto permite explicar como la energía de red de las sales es fuertemente debilitada por la presencia del solvente, como factor principal en la obtención de las especies, por encima de la energía de interacción con el ligando. - Descripción de algunas características químicas importantes. La contribución de los espectros de resonancia magnética nuclear resulta decisiva para la caracterización de los compuestos. Una descripción en detalle de las particularidades en el cálculo de los desplazamientos químicos para espectros de RMN es revisado en un apartado puramente teórico, especialmente para los métodos DFT. La activación del enlace C-H del carbono apical en el ligando [{TiCp*(-O)}3(3-CH)] durante la formación de estructuras diméricas fue seguida mediante espectroscopia RMN de 13C. Los grandes cambios experimentados en los desplazamientos químicos entre las especies protonadas y no protonadas han sido descritos y racionalizados perfectamente mediante cálculos teóricos. Los resultados obtenidos corroboran las suposiciones experimentales y proporcionan una visión muy clara de los procesos electrónicos que conducen a estos resultados. El carácter predictivo de estos estudios para con otras especies es claro, no obstante cuantitativamente hablando se encuentran dificultades a la hora de atribuir todos los desplazamientos.Fruto de los excelentes resultados obtenidos en la descripción de los valores de RMN para los compuestos cubánicos, estos estudios se han ampliado a otros campos de interés para nuestro grupo de trabajo. Una sección, en parte diferente a la estructura global de la tesis, se ha dedicado ha mostrar estos primeros pasos a la hora de examinar las capacidades de los métodos DFT para computar los desplazamientos en núcleos de 183W en compuestos de Keggin. Nos encontramos ante unas mayores dificultades a la hora de reproducir los espectros experimentales, y gran parte de nuestros esfuerzos se han centrado en tratar de buscar la forma de trabajo más adecuada en términos de precisión y de coste computacional. La investigación y el interés continúan abiertos en un campo que necesita nuevas revisiones, sobre todo a la hora de racionalizar las posibles fuentes de error.Las importantes características catalíticas de los sulfuros de molibdeno son objeto de estudio en la segunda parte de la tesis. El estudio teórico intentará aclarar ciertos aspectos confusos en la mecanistica asociada con las reacciones de estos compuestos. Estos complejos dinucleares de molibdeno con ligandos puente de azufre son una de las familias que posee una gran flexibilidad estructural y electrónica. Parte de los posibles isómeros del compuesto tipo [(CpMo)-S2]2 han sido estudiados, prestando gran interés al intercambio electrónico metal ligando con el cambio de estructura. Ejemplos de estructuras cerradas (a-b) y abiertas (c-d) para el complejo La capacidad de los complejos del sulfuro de activar el hidrógeno molecular y de catalizar la reducción del substrato por el hidrógeno es particularmente relevante en la química. En especial los procesos relacionados con la activación de hidrógeno y posterior reducción de un sustrato ligado a los azufre puente son analizados; y en particular aquellos relacionados con la estructura electrónica del catalizador y del substrato. En estos estudios se pone de manifiesto la importancia catalizadora del metal, sirviendo como puente para protones en la reducción. A su vez se muestra como la naturaleza del sustrato resulta decisiva a la hora de observar una eliminación de hidrógeno molecular o una obtención del substrato reducido.Tarragona, 2004 J. Gracia, The overall framework of this report aims to summarize the work we have done over the past four years. Conceptually, this thesis is divided into three parts. The nucleus is based on a joint project with prof. Mena, of the University of Alcalá, whose group is involved in the synthesis and characterization of new aza- and oxo- titanium cubanes. These families of compounds are basically obtained from preorganized titanium tridentate ligands which can incorporate almost all the metals of the periodic table and yield the corresponding heterometallic cubanes. In this respect, the theoretical study is based on and adapted from the progress in the laboratory work. Practically every section in this part starts by describing the experimental data available for the specific system studied when we began the analysis. Then we go on to describe the theoretical study and attempt to involve the reader in the problems discussed. As a consequence of the advance in the experimental work, NMR spectra are used to characterize the new compounds. This leads us to initiate studies in the computational simulation of NMR chemical shifts. The most theoretical part of this report is an assimilation of these studies. The excellent results obtained for the cubane compounds enabled us to extend the knowledge acquired to other interesting fields and our group has started a study of the NMR shielding tensors in polyoxometalate compounds. The third part of the thesis focuses on some molybdenum-sulphide clusters and their activity as catalysts.Chapters 3 and 4 focuse on the electronic structure of the new titanium cubane compounds recently synthesized by Mena et al. We work parallel to an experimental group to compare and contrast the theoretical and experimental data, and so establish the base chemistry of these new compounds. In this sense, the various reaction energies were studied, and the compounds and their possible isomers were characterised by means of DFT methods. Particular emphasis is paid to the properties of incomplete Ti3 core cubane tridentate ligands (precubanes) as bases for obtaining cubanes. The electronic structure, bonding energies, electron transfer processes and reactivity in the titanium Ti3 core of the metal clusters are studied.The reaction of the azatitanium compound with some titanium derivatives leads to nitrocubane formation (see Scheme 1.3). This reaction forms a cubane compound by adding the fourth vertex to a structure that becomes a precubane. Scheme 1.3. Reaction of with Chapter 5 summarizes the work carried out during a six-month stay in Dr. John E. McGrady's group, which uses density functional theory to explore problems of structure, bonding and reactivity in inorganic compounds. The main focus of the research is metal-metal bonding in cluster compounds. Transition metals have a prominent position in catalysis, both in industrial and biological contexts, and the ultimate goal is to understand the part played by the metal and its ligand environment in facilitating a particular chemical transformation. Chapter 5 studies the electronic structure of the core catalysts and the mechanism of their, unresolved, catalytic activity. The various possible isomers with the generic formula were studied, and the energy of the electron transfer between the metallic centres and the sulphide ligands, so important in the catalytic process, was investigated in depth. Subsequently, the mechanism of the hydrogen activation reaction promoted by these bi-molybdenum compounds (Equation 1.1) was studied, and the nature of the different reaction pathways was elucidated.[(CpMo(-S))2(S2CH2)] promotes the hydrogenation of alkynes to cis alkenes, allenes to alkenes, and ketenes to aldehydes and the hydrogenolysis of carbon disulphide to hydrogen sulphide and thioformaldehide. The mechanisms of hydrogen interaction with these complexes have not been established. It is apparent that the sulphide ligands play a role in hydrogen coordination, and this ligand reactivity was a dominant characteristic throughout the study of these dinuclear molybdenum systems. Equation 1.1

has been addressed with quantum chemicalcalculations on large embedded clusters. We find a charge ordered state for the crystal structure reported byRadaelli et al. [Phys. Rev. B 55, 3015 (1997)] and Zener polaron formation in the crystal structure withequivalent Mn sites proposed by Daoud-Aladineet al. [Phys. Rev. Lett. 89, 097205 (2002)]. Important O toMn charge transfer effects are observed for the Zener polaron.DOI: 10.1103/PhysRevB.70.235104 PACS number(s): 75.47.Lx, 71.15.Ap, 71.27.1aI. INTRODUCTION

We explore the ability of the recently established quasilocal density functional theory for describing the isoscalar giant monopole resonance. Within this theory we use the scaling approach and perform constrained calculations for obtaining the cubic and inverse energy weighted moments (sum rules) of the RPA strength. The meaning of the sum rule approach in this case is discussed. Numerical calculations are carried out using Gogny forces and an excellent agreement is found with HF + RPA results previously reported in literature. The nuclear matter compression modulus predicted in our model lies in the range 210-230 MeV which agrees with earlier findings. The information provided by the sum rule approach in the case of nuclei near the neutron drip line is also discussed., 10 pages, LaTeX

El nitrógeno presenta propiedades electrónicas como polarizabilidad y electronegatividad, así como características cristaloquímicas -radios iónicos, índices de coordinación- muy próximas a las del oxígeno. Ello permite que ambos aniones puedan sustituirse mutuamente en las mismas posiciones cristalográficas, formando disoluciones sólidas. En este sentido nos podemos plantear diseñar nuevos edificios cristalinos de fases nitruradas de metales de transición que presenten estructuras similares a las de los óxidos con aplicaciones por sus propiedades magnéticas, catalíticas, conductividad electrónica o iónica, superconductividad, como materiales para baterías, como dieléctricos, ferroeléctricos, etc.El trabajo experimental realizado ha permitido aislar con éxito dos términos de una nueva familia de oxinitruros de Ruddlesden-Popper de estroncio y niobio. Ésta se formuló como un intercrecimiento de n capas de tipo perovsquita que contienen un nitrógeno por capa [SrNbO2N] y una capa de tipo cloruro sódico [SrO], es decir [SrO][SrNbO2N]n. Dicha formulación inicial se realizó por analogía con los oxinitruros conocidos SrNbO2N y Sr2TaO3N, si bien se esperaba poder modificar el estado de oxidación formal del niobio desde +5 hacia valores inferiores mediante dopaje con metales electropositivos en la posición del estroncio, o por variación de la relación N/O, incluyendo la posible existencia de vacantes aniónicas. Se han obtenido como fases puras los términos n= 1 y n= 2 mediante la reacción:n+1 SrCO3 + n/2 Nb2O5 + n NH3 _ Srn+1NbnO2n+1Nn + 3n/2 H2O + (n+1) CO2Además de los términos n= 1 y n= 2 se han observado miembros de la familia con n= 3 y 4 como defectos extensos en imágenes de microscopía electrónica de alta resolución. Asimismo se ha podido preparar el nuevo compuesto Sr3Ta2O5N2 mediante un procedimiento análogo al de las fases de niobio, lo que teniendo en cuenta la existencia del término n= 1 (Sr2TaO3N), permite formular la familia homóloga de tántalo [SrO][SrTaO2N]n.El estudio de estas fases mediante difracción de electrones conduce al grupo espacial I4/mmm, que es el de más alta simetría de entre los observados en compuestos de tipo Ruddlesden-Popper.Hasta el momento, los oxinitruros preparados no presentan ninguna transición superconductora entre 300 y 4 K, ni carácter metálico. ¿Por qué los óxidos con valencia mixta d0-d1 suelen ser metálicos y los oxinitruros preparados no presentan este comportamiento? A priori parece que ambos tipos de compuestos deberían mostrar las mismas propiedades físicas ya que en los dos casos tenemos una ocupación parcial de las bandas del bloque t2g del metal y estas bandas deben presentar una buena deslocalización. Para entender mejor las propiedades de transporte en los oxinitruros preparados, y debido a que por otro lado, en los óxidos laminares con configuración electrónica d0 se plantea a menudo la posibilidad del dopaje para variar el estado de oxidación formal del metal de transición, se ha desarrollado un modelo cualitativo que permite la comprensión de las propiedades de transporte de sistemas laminares relacionados con la estructura perovsquita para contages electrónicos entre d0 y d1. Inicialmente se analiza la estructura electrónica correspondiente al caso hipotético de un sistema construido a partir de octaedros ideales y posteriormente se analizan distintos casos reales de estructuras con dos, tres y cuatro capas de octaedros en los que se estudia el efecto que tienen distintos factores cristaloquímicos sobre la naturaleza y la dispersión de las bandas.Este estudio nos aporta una herramienta muy útil para la predicción de la naturaleza de los niveles parcialmente ocupados que determinan las propiedades de transporte de este tipo de compuestos, conociendo su estructura y número de electrones. Asimismo, a partir de los resultados de este análisis podemos entender porque los oxinitruros preparados por el momento no presentan comportamiento metálico., Nitrogen presents some properties like polarizability, electronegativity, ionic radii and coordination numbers quite similar to oxygen. This allows that both anions can be exchanged in the same crystallographic position, creating solid disolutions. Following this approach we can design the formation of new transition metal nitride compounds with analogous structures to their parent oxides. The substitution of oxygen by nitrogen will promote the modification of their physical properties (magnetic, catalytic, electronic or ionic conductivity, superconductivity, applications as dielectric materials, electrodes for batteries, ferroelectrics,...).The experimental work has allowed us to synthesize two members of the new family of Ruddlesden-Popper strontium niobium oxynitrides. This compounds consist of an intergrowth of n perovskite layers with one nitrogen per layer [SrNbO2N] and a layer of [SrO] with NaCl structure. So we have the general formula [SrO][SrNbO2N]n. This materials were prepared following the approach used for the already known SrNbO2N and Sr2TaO3N oxynitrides. With the aim of modifying the niobium oxidation state from +5 to lower values, we carried out some experiments in order to substitute the strontium for lanthanum and to change the N/O ratio. We have obtained as pure phases the members n= 1 and n= 2 following the reaction:n+1 SrCO3 + n/2 Nb2O5 + n NH3 _ Srn+1NbnO2n+1Nn + 3n/2 H2O + (n+1) CO2Apart from the n= 1 and n= 2 members we have observed the n= 3 and n= 4 phases as extended intergrowths in high resolution transmission electron microscopy images. We have also been able to synthesize the new compound Sr3Ta2O5N2 using the ammonolysis system. Since the n= 1 phase, Sr2TaO3N, had already been prepared, we could establish the new family [SrO][SrTaO2N]n.The space group I4/mmm was determined by electron diffraction. This group has the highest symmetry among the observed for the Ruddlesden-Popper phases.Up to now, the prepared oxynitrides are not metallic and magnetic measurements do not show any superconducting transition down to 4 K. Why the mixed valence oxides are often metallic and the prepared oxynitrides do not have this behaviour? It looks like both compounds would present the same physical properties since they have partial occupation of the t2g bands, and this bands would have a good delocalization. In order to understand the transport properties of the prepared oxynitrides and due to the current interest in the intercalation of alkali-metal cations in the layered oxide systems, we have developed a qualitative model that is useful to understand the transport properties of laminar perovskite related systems with electronic configurations d0-d1. In a first stage the electronic structure of an idealized system (regular octahedrons) is constructed. Then, several compounds with n= 2, n= 3 and n= 4 are analyzed. We have studied the effect of different factors on the nature and dispersion of the bands.With this study we have developed a really useful tool to predict the nature of the partially occupied bands that determine the transport properties of this type of compounds. We just need to know the crystal structure and the electron count. It has also been useful to understand the properties of the prepared oxynitrides.

Oxygen vacancies in metal oxides are known to determine their chemistry and physics. The properties of neutral oxygen vacancies in metal oxides of increasing complexity (MgO, CaO, alpha-Al2O3, and ZnO) have been studied using density functional theory. Vacancy formation energies, vacancy-vacancy interaction, and the barriers for vacancy migration are determined and rationalized in terms of the ionicity, the Madelung potential, and lattice relaxation. It is found that the Madelung potential controls the oxygen vacancy properties of highly ionic oxides whereas a more complex picture arises for covalent ZnO.

The electronic and magnetic structures of the LaMnO3 compound have been studied by means of periodic calculations within the framework of spin polarized hybrid density-functional theory. In order to quantify the role of approximations to electronic exchange and correlation three different hybrid functionals have been used which mix nonlocal Fock and local Dirac-Slater exchange. Periodic Hartree-Fock results are also reported for comparative purposes. The A-antiferromagnetic ground state is properly predicted by all methods including Hartree-Fock exchange. In general, the different hybrid methods provide a rather accurate description of the band gap and of the two magnetic coupling constants, strongly suggesting that the corresponding description of the electronic structure is also accurate. An important conclusion emerging from this study is that the nature of the occupied states near the Fermi level is intermediate between the Hartree-Fock and local density approximation descriptions with a comparable participation of both Mn and O states.

Incompressible (magic) states of vertically coupled quantum dots submitted to strong magnetic fields such that only the lowest Landau level is relevant are studied within an exact diagonalization calculation for N=3, 5 and 6, electrons. We find that the sequences of total angular momentum M for which incompressible states exists depend on the interplay between the inter-dot hopping parameter \Delta_t and the inter-dot distance d. For d of the order of the magnetic length and for all values of \Delta_t, we conclude that, in contrast to previous claims, the incompressible states appear at magic values of M which do not differ from those obtained for a single dot, namely M=N(N-1)/2+jN where j is a positive integer number. For large inter-dot distance and simultaneously small inter-dot hopping parameter, new sequences of magic values of $M$ are observed. These new sequences can be easily understood in terms of a transition regime towards a system of two decoupled single dots. However, important differences in the nature of the incompressible ground states are found with respect to those of a single dot., Comment: 23 pages, 11 figures; discussion improved, references added, journal version

Thomas-Fermi theory is developed to evaluate nuclear matrix elements averaged on the energy shell, on the basis of independent particle Hamiltonians. One- and two-body matrix elements are compared with the quantal results and it is demonstrated that the semiclassical matrix elements, as function of energy, well pass through the average of the scattered quantum values. For the one-body matrix elements it is shown how the Thomas-Fermi approach can be projected on good parity and also on good angular momentum. For the two-body case the pairing matrix elements are considered explicitly., Comment: 15 pages, REVTeX, 6 ps figures; changed content

El objetivo de este trabajo de tesis fue el estudio a nivel molecular de la interacción dela melatonina (N-acetil-S-metoxitriptamina) con dos radicales libres de relevanciabiológica, el radical oxhidrilo (OH·) y el óxido nítrico (NO). Para el desarrollo del presente trabajo se analizaron estas interacciones químicas desdeun enfoque teórico, mediante técnicas de simulación computacional, desde un enfoqueexperimental, a través del estudio de las mismas en condiciones aisladas y controladas,y a través de la evaluación de los alcances fisiológicos de las reacciones propuestas. Para evaluar las interacciones con los diferentes blancos se analizó, en primer término,la superficie de energía potencial de la melatonina mediante técnicas de dinámicamolécular basadas en campos de fuerzas clásicos y métodos semiempíricos. Se prestóespecial atención a los aspectos relacionados con su libertad conformacional en vacío yen solución acuosa. Asimismo, se analizó la dependencia de las propiedadesmoleculares con la conformación. La reacción con el radical oxhidrilo se estudió mediante técnicas de estructuraelectrónica, evaluando los posibles mecanismos de reacción y realizando una exhaustivacaracterización de los intermediarios. El estudio de la interacción con NO se puede dividir en dos partes: i) la identificación ycaracterización de los productos de reacción y la elucidación de los mecanismosoperantes en diversos medios; y ii) el estudio del efecto de la melatonina sobre labiosíntesis de NO en la retina de hámster. Finalmente, mediante el uso de técnicas de resonancia magnética nuclear y de dinámicamolecular, se realizó un estudio detallado de la interacción entre la melatonina y lacalmodulina, una proteína con probado efecto estimulatorio en la biosíntesis del NO. The goal of this thesis was the study at a molecular level of the interactions of melatonin (N-Acetyl-5-metoxytriptamine) with two free radicals of biological relevance, hydroxyl (OH·) radical and nitric oxide (NO). The evaluation of the different interactions has been performed by a theoreticalapproach using molecular modeling tools; through the study of these reactions inisolated and controlled conditions, and finally by the evaluation of their physiologicalrelevance. In order to evaluate the interactions with these different targets, the potential energysurface of melatonin has been analyzed by classical molecular dynamics andsemiempirical electronic structure methodologies. Special attention has been paid to theconformational behavior in vacuum and aqueous solution. Moreover, the influence ofconformation on several properties has been studied. The reaction with OH· has been analyzed with electronic structure methods. Feasiblereaction mechanisms have been evaluated along with a thorough characterization of theintermediates. The research on the interaction with NO consisted of: i) the identification andcharacterization of the products, and the elucidation of the mechanisms operative indifferent environments ii) by the analysis of the effect of melatonin on NO biosynthesisin the hamster retina. Finally, by means of nuclear magnetic resonance and molecular dynamics techniques, adetailed study of the interaction of melatonin with calmodulin, a stimulatory protein of NO biosynthesis has been carried out. Fil: Turjanski, Adrián G.. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina.

We carry out a self-consistent analytical theory of unipolar current and noise properties of metal-semiconductor-metal structures made of highly resistive semiconductors in the presence of an applied bias of arbitrary strength. By including the effects of the diffusion current we succeed to study the whole range of carrier injection conditions going from low level injection, where the structure behaves as a linear resistor, to high level injection, where the structure behaves as a space charge limited diode. We show that these structures display shot noise at the highest voltages. Remarkably the crossover from Nyquist noise to shot noise exhibits a complicate behavior with increasing current where an initial square root dependence (double thermal noise) is followed by a cubic power law., Comment: 10 pages, 8 figures. Accepted for publication in Journal of Applied Physics (Scheduled 1 January 2003)

The role of the bridging ligand on the effective Heisenberg coupling parameters is analyzed in detail. This analysis strongly suggests that the ligand-to-metal charge transfer excitations are responsible for a large part of the final value of the magnetic coupling constant. This permits to suggest a new variant of the Difference Dedicated Configuration Interaction (DDCI) method, presently one of the most accurate and reliable for the evaluation of magnetic effective interactions. This new method treats the bridging ligand orbitals mediating the interaction at the same level than the magnetic orbitals and preserves the high quality of the DDCI results while being much less computationally demanding. The numerical accuracy of the new approach is illustrated on various systems with one or two magnetic electrons per magnetic center. The fact that accurate results can be obtained using a rather reduced configuration interaction space opens the possibility to study more complex systems with many magnetic centers and/or many electrons per center., Comment: 7 pages, 4 figures

The magnetic coupling constant of selected cuprate superconductor parent compounds has been determined by means of embedded cluster model and periodic calculations carried out at the same level of theory. The agreement between both approaches validates the cluster model. This model is subsequently employed in state-of-the-art configuration interaction calculations aimed to obtain accurate values of the magnetic coupling constant and hopping integral for a series of superconducting cuprates. Likewise, a systematic study of the performance of different ab initio explicitly correlated wave function methods and of several density functional approaches is presented. The accurate determination of the parameters of the t-J Hamiltonian has several consequences. First, it suggests that the appearance of high- Tc superconductivity in existing monolayered cuprates occurs with J/t in the 0.20‐0.35 regime. Second, J/t50.20 is predicted to be the threshold for the existence of superconductivity and, third, a simple and accurate relationship between the critical temperatures at optimum doping and these parameters is found. However, this quantitative electronic structure versus Tc relationship is only found when both J and t are obtained at the most accurate level of theory.

We report two new analytical fits of the ground potential energy surface (PES) (2A') and the first excited PES (4A') involved into the title reaction and its reverse, using ab initio electronic structure calculations from papers I and II along with new grids of ab initio points by means of the Second-Order Perturbation Theory on CASSCF wave function (CASPT2 (17,12) G2/aug-cc-pVTZ) reported here (1250 points for the 2A' PES and 910 points for the 4A' PES). Some experimental data were also introduced to better account for the exoergicity and the experimental rate constant at 300 K. The final root-mean-square deviations of the fits were 1.06 and 1.67 kcal/mol for 2A' and the 4A' PESs, respectively, for the NOO Cs-abstraction and insertion regions of the PESs. Thermal rate constants were calculated (300-5000 K) for both the direct and reverse reactions by means of the variational transition state theory with the inclusion of a microcanonical optimized multidimensional tunneling correction, obtaining a very good agreement with the experimental data within all the temperature range. The new analytical 2A' PES presents several stationary points not introduced in previous analytical surfaces, and describes accurately the NO2 (X 2A1) minimum, which seems to be very accessible according to the trajectories run in a preliminary quasiclassical trajectory study. The new analytical 4A' PES has a lower energy barrier than the previous one, which increases significantly the contribution of this PES to the total rate constant at high temperatures. Moreover, the new analytical PESs not only describe accurately the Cs-regions of the NOO system but also the ONO C2v- or near C2v-regions.

Electron transport in a self-consistent potential along a ballistic two-terminal conductor has been investigated. We have derived general formulas which describe the nonlinear current-voltage characteristics, differential conductance, and low-frequency current and voltage noise assuming an arbitrary distribution function and correlation properties of injected electrons. The analytical results have been obtained for a wide range of biases: from equilibrium to high values beyond the linear-response regime. The particular case of a three-dimensional Fermi-Dirac injection has been analyzed. We show that the Coulomb correlations are manifested in the negative excess voltage noise, i.e., the voltage fluctuations under high-field transport conditions can be less than in equilibrium., Comment: 16 pages, 10 figs; minor corrections

We investigate the dissociation of few-electron circular vertical semiconductor double quantum dot artificial molecules at 0 T as a function of interdot distance. Slight mismatch introduced in the fabrication of the artificial molecules from nominally identical constituent quantum wells induces localization by offsetting the energy levels in the quantum dots by up to 2 meV, and this plays a crucial role in the appearance of the addition energy spectra as a function of coupling strength particularly in the weak coupling limit., Accepted for publication in Phys. Rev. Lett

A series of new compounds has been synthesized by insertion of alkali or alkaline earth-metals in chalcopyrite, CuFeS2. Their crystal structures vary from layered arrangements of tetrahedra in a trigonal (LiCuFeS2, NaCuFeS2) or a tetragonal symmetry (KCuFeS2, CsCuFeS2), to three-dimensional cubic framework (Ba6Cu12Fe13S 27). Despite these differences, the synthesized compounds follow a common structural pattern: the sulfur and M atoms (M= Li, Na, K, Cs, or Ba) are ordered in a distorted face-centered-cubic lattice, where all tetrahedral holes surrounded by S atoms are occupied by the transition metal elements. The tetrahedral holes surrounded by both S atoms and at least one M element are empty. The band structures of these compounds are discussed in the framework of an extended Hückel Hamiltonian Una serie de nuevos compuestos han sido sintetizados por inserción de iones de metales alcalinos o alcalinos-térreos en calcopirita. Sus estructuras cristalinas varían desde un ordenamiento bidimensional de tetraedros con simetría trigonal (LiCuFeS2, NaCuFeS2) o con simetría tetragonal (KCuFeS2, CsCuFeS2), hasta un ordenamiento cúbico tridimensional (Ba6Cu 12Fe13S27). A pesar de estas diferencias, los compuestos sintetizados siguen un patrón estructural común: los átomos de azufre y del tipo M (M= Li, Na, K, Cs, or Ba ) están ordenados en una red cúbica de cara centrada distorsionada, donde todos los huecos tetraédricos que están rodeados por átomos de azufre, son ocupados por Cu o Fe . Los huecos tetraédricos que están rodeados por átomos de S y al menos un elemento del tipo M están vacíos. La estructura de bandas de estos compuestos se calcularon por el método de extended Hückel

A self-consistent theory of shot noise in ballistic two-terminal conductors under the action of long-range Coulomb correlations is presented. Analytical formulas for the electron distribution function and its fluctuation along the conductor, which account for the Coulomb correlations, have been derived. Based upon these formulas, the current-noise reduction factor has been obtained for biases ranging from thermal to shot-noise limits as dependent on two parameters: the ratio between the length of the sample and the Debye screening length \lambda=d/L_D and the applied voltage qU/k_BT. The difference with the formulas for a vacuum diode is discussed., Comment: 21 pages, 11 figs, minor changes

Ab initio cluster model wave functions are used to predict the existence of localized excited states in MgO, Al2O3, and SiO2 arising from metal 2p core-level excitations. Theoretical values obtained at different levels of theory result in a quantitative agreement with experiment, and the use of different models permits us to quantify the different contributions to the final excitation energy. The most important contribution is atomic in nature; a meaningful zero-order approximation is that in MgO and Al2O3 the exciton can be assigned to a M(2p6)→M(2p53s1)-like excitation, where M5Mg or Al. For the atomic models, the singlet-triplet exchange in the excited configuration is in good agreement with experiment. In addition, the solid-state effects on this exchange energy predicted by experiment are well reproduced by the cluster models representing MgO and SiO2, whereas a less clear situation appears in Al2O3. The open-shell orbital in the final state has, however, important contributions from the ions near the atomic site where excitation occurs. Nevertheless, the final state appears to be localized in space without any a priori assumption, the localization following from the holeparticle interaction implicitly induced in the final-state wave function. The Madelung field reduces the excitation energy with respect to the atomic value; the effect of neighboring atoms, mainly Pauli repulsion, acts in the opposite way; and electronic correlation effects decrease it again. In agreement with the covalent nature of SiO2, the exciton cannot be simply understood as arising from a Si(2p6)→Si(2p53s1) in a fully oxidized Si cation.

The ab initio periodic unrestricted Hartree-Fock method has been applied in the investigation of the ground-state structural, electronic, and magnetic properties of the rutile-type compounds MF2 (M=Mn, Fe, Co, and Ni). All electron Gaussian basis sets have been used. The systems turn out to be large band-gap antiferromagnetic insulators; the optimized geometrical parameters are in good agreement with experiment. The calculated most stable electronic state shows an antiferromagnetic order in agreement with that resulting from neutron scattering experiments. The magnetic coupling constants between nearest-neighbor magnetic ions along the [001], [111], and [100] (or [010]) directions have been calculated using several supercells. The resulting ab initio magnetic coupling constants are reasonably satisfactory when compared with available experimental data. The importance of the Jahn-Teller effect in FeF2 and CoF2 is also discussed.

The results are presented of a combined periodic and cluster model approach to the electronic structure and magnetic interactions in the spin-chain compounds Ca2CuO3 and Sr2CuO3. An extended t-J model is presented that includes in-chain and interchain hopping and magnetic interaction processes with parameters extracted from ab initio calculations. For both compounds, the in-chain magnetic interaction is found to be around -240 meV, larger than in any of the other cuprates reported in the literature. The interchain magnetic coupling is found to be weakly antiferromagnetic, -1 meV. The effective in-chain hopping parameters are estimated to be ~650 meV for both compounds, whereas the value of the interchain hopping parameter is 30 meV for Sr2CuO3 and 40 meV for Ca2CuO3, in line with the larger interchain distance in the former compound. These effective parameters are shown to be consistent with expressions recently suggested for the Néel temperature and the magnetic moments, and with relations that emerge from the t-J model Hamiltonian. Next, we investigate the physical nature of the band gap. Periodic calculations indicate that an interpretation in terms of a charge-transfer insulator is the most appropriate one, in contrast to the suggestion of a covalent correlated insulator recently reported in the literature.

We investigate the current injection into a ballistic conductor under the space-charge limited regime, when the distribution function of injected carriers is an arbitrary function of energy F_c(epsilon). The analysis of the coupled kinetic and Poisson equations shows that the injected current fluctuations may be essentially suppressed by Coulomb correlations, and the suppression level is determined by the shape of F_c(epsilon). This is in contrast to the time-averaged quantities: the mean current and the spatial profiles are shown to be insensitive to F_c(epsilon) in the leading-order terms at high biases. The asymptotic high-bias behavior for the energy resolved shot-noise suppression has been found for an arbitrary (non-Poissonian) injection, which may suggest a new field of investigation on the optimization of the injected energy profile to achieve the desired noise-suppression level., extended version 4 -> 8 pages, examples and figure added

Recent improvements in the determination of the running of the fine-structure constant also allow an update of the hadronic vacuum-polarization contribution to the Lamb shift. We find a shift of -3.40(7) kHz to the 1S level of hydrogen. We also comment on the contribution of this effect to the determination by elastic electron scattering of the r.m.s. radii of nuclei., Comment: 7 pages, latex, 1 figure -- Submitted to Phys. Rev. A -- epsfig.sty required