Ground and excited states of KNiF3: An ab initio cluster-model approach

Finite cluster models and a variety of ab initio wave functions have been used to study the electronic structure of bulk KNiF3. Several electronic states, including the ground state and some charge-transfer excited states, have been considered. The study of the cluster-model wave functions has permitted an understanding of the nature of the chemical bond in the electronic ground state. This is found to be highly ionic and the different ionic and covalent contributions to the bonding have been identified and quantified. Finally, we have studied the charge-transfer excited states leading to the optical gap and have found that calculated and experimental values are in good agreement. The wave functions corresponding to these excited states have also been analyzed and show that although KNiF3 may be described as a ligand-to-metal charge-transfer insulator there is a strong configuration mixing with the metal-to-metal charge-transfer states.

Performance of correlation functionals in ab initio chemisorption cluster-model calculations: Alkali metals on Si(111)

The performance of different correlation functionals has been tested for alkali metals, Li to Cs, interacting with cluster models simulating different active sites of the Si(111) surface. In all cases, the ab initio Hartree-Fock density has been obtained and used as a starting point. The electronic correlation energy is then introduced as an a posteriori correction to the Hartree-Fock energy using different correlation functionals. By making use of the ionic nature of the interaction and of different dissociation limits we have been able to prove that all functionals tested introduce the right correlation energy, although to a different extent. Hence, correlation functionals appear as an effective and easy way to introduce electronic correlation in the ab initio Hartree-Fock description of the chemisorption bond in complex systems where conventional configuration interaction techniques cannot be used. However, the calculated energies may differ by some tens of eV. Therefore, these methods can be employed to get a qualitative idea of how important correlation effects are, but they have some limitations if accurate binding energies are to be obtained.

Rigorous characterization of oxygen vacancies in ionic oxides

Charged and neutral oxygen vacancies in the bulk and on perfect and defective surfaces of MgO are characterized as quantum-mechanical subsystems chemically bonded to the host lattice and containing most of the charge left by the removed oxygens. Attractors of the electron density appear inside the vacancy, a necessary condition for the existence of a subsystem according to the atoms in molecules theory. The analysis of the electron localization function also shows attractors at the vacancy sites, which are associated to a localization basin shared with the valence domain of the nearest oxygens. This polyatomic superanion exhibits chemical trends guided by the formal charge and the coordination of the vacancy. The topological approach is shown to be essential to understand and predict the nature and chemical reactivity of these objects. There is not a vacancy but a coreless pseudoanion that behaves as an activated host oxygen.

Ground- and excited-state properties of M-center oxygen vacancy aggregates in the bulk and the surface of MgO

Aggregates of oxygen vacancies (F centers) represent a particular form of point defects in ionic crystals. In this study we have considered the combination of two oxygen vacancies, the M center, in the bulk and on the surface of MgO by means of cluster model calculations. Both neutral and charged forms of the defect M and M+ have been taken into account. The ground state of the M center is characterized by the presence of two doubly occupied impurity levels in the gap of the material; in M+ centers the highest level is singly occupied. For the ground-state properties we used a gradient corrected density functional theory approach. The dipole-allowed singlet-to-singlet and doublet-to-doublet electronic transitions have been determined by means of explicitly correlated multireference second-order perturbation theory calculations. These have been compared with optical transitions determined with the time-dependent density functional theory formalism. The results show that bulk M and M+ centers give rise to intense absorptions at about 4.4 and 4.0 eV, respectively. Another less intense transition at 1.3 eV has also been found for the M+ center. On the surface the transitions occur at 1.6 eV (M+) and 2 eV (M). The results are compared with recently reported electron energy loss spectroscopy spectra on MgO thin films.

Surface structure and stability of PdZn and PtZn alloys: Density-functional slab model studies

Geometric parameters of binary (1:1) PdZn and PtZn alloys with CuAu-L10 structure were calculated with a density functional method. Based on the total energies, the alloys are predicted to feature equal formation energies. Calculated surface energies of PdZn and PtZn alloys show that (111) and (100) surfaces exposing stoichiometric layers are more stable than (001) and (110) surfaces comprising alternating Pd (Pt) and Zn layers. The surface energy values of alloys lie between the surface energies of the individual components, but they differ from their composition weighted averages. Compared with the pure metals, the valence d-band widths and the Pd or Pt partial densities of states at the Fermi level are dramatically reduced in PdZn and PtZn alloys. The local valence d-band density of states of Pd and Pt in the alloys resemble that of metallic Cu, suggesting that a similar catalytic performance of these systems can be related to this similarity in the local electronic structures.

Alignment of hexatic langmuir monolayers under shear

We have studied the structural changes that fatty acid monolayers in the Ov phase undergo when a simple shear flow is imposed. A strong coupling is revealed by the changes in domain structure that are observable using Brewster angle microscopy, suggesting the possibility of shear alignment. The dependence of the alignment on the molecular polar tilt proves that the mechanism is different than in nematic liquid crystals. We argue that the degenerate lattice symmetry lines of the underlying pseudohexagonal lattice align in the flow direction, and we explain the observed alignment angle using geometrical arguments.

Self-organizing propagation patterns from dynamic self-assembly in monolayers

Propagation of localized orientational waves, as imaged by Brewster angle microscopy, is induced by low intensity linearly polarized light inside axisymmetric smectic-C confined domains in a photosensitive molecular thin film at the air/water interface (Langmuir monolayer). Results from numerical simulations of a model that couples photoreorientational effects and long-range elastic forces are presented. Differences are stressed between our scenario and the paradigmatic wave phenomena in excitable chemical media.

Resposta espectral de solos em razão do ângulo de visada, da umidade e da rugosidade superficial

Este trabalho teve por objetivo avaliar as variações do fator de refletância bidirecional (FRB) de três séries de solo (McAllister, Stronghold e Epitaph) da microbacia experimental de Walnut Gulch (Arizona, EUA) em razão do ângulo de visada, da rugosidade superficial e do teor de umidade. Foram consideradas as faixas espectrais do visível e do infravermelho próximo e médio presentes no sensor TM, e os resultados foram expressos em termos de FRB em relação à resposta no Nadir (FRB relativo). O anisotropismo variou de solo para solo e foi maior nas menores faixas espectrais, nos ângulos de visada maiores localizados na direção do retroespalhamento, nos ângulos solar-zenitais maiores, e na condição de solo seco. No solo Epitaph (único solo submetido ao estudo de rugosidade) o anisotropismo foi também maior na superfície mais rugosa. Entretanto, uma melhor diferenciação entre as superfícies lisa e rugosa do solo Epitaph foi obtida na direção do espalhamento da energia refletida. Diferenças na escala e nos métodos de obtenção dos dados são apontadas como causas do realce do comportamento anisotrópico dos dados obtidos em condições de laboratório, em comparação com os dados de campo.

Interações silício-fósforo em solos cultivados com eucalipto em casa de vegetação

Este trabalho teve o objetivo de avaliar as interações Si-P em dois solos, por meio do estado nutricional de P em mudas de Eucalyptus grandis sob efeito de aplicação de Si. Foram conduzidos dois experimentos em casa de vegetação, utilizando como substratos as camadas superficiais (0-20 cm de profundidade) de um Latossolo Vermelho-Escuro fase cerrado e de um Cambissolo fase campo cerrado da zona fisiográfica Campos das Vertentes, MG . Cada solo foi submetido a três incubações seqüenciais: CaCO3 + MgCO3 para manter o pH em torno de 6, fertilização básica, incluindo o P em dose única, para manter 0,2 mg L-1 de P em solução e seis doses de Si (CaSiO3) definidas com base na dose de P. Foram avaliados a produção de matéria seca da parte aérea (MSPA), conteúdo de P e Si na MSPA e frações fosfatadas e fosfatase ácida em folhas apicais aos 60, 90 e 120 dias após o transplantio das mudas para os vasos. Ajustaram-se superfícies de resposta para essas variáveis em razão das doses de Si e das épocas. Mudas cultivadas no Cambissolo tiveram ganho de 15,25% no conteúdo de P na MSPA. Frações fosfatadas e atividade da fosfatase ácida em plantas não mostraram sensibilidade para avaliar a interação Si-P nos dois solos.

Relações solo-superfície geomórfica e evolução da paisagem em uma área do Planalto Central Brasileiro

Com base em levantamento pedológico de reconhecimento de alta intensidade, foram investigadas relações pedogeomorfológicas em uma área do Planalto Central Brasileiro, com vistas à predição de atributos e distribuição dos solos em áreas vizinhas carentes de mapas pedológicos. Três superfícies geomórficas, com distintos padrões de espacialização de solos, foram identificadas. Na mais elevada, a distribuição dos solos é estreitamente relacionada à variação do regime hídrico ao longo das encostas. Ocorrem Latossolo Vermelho (LV), Latossolo Vermelho-Amarelo (LVA), Latossolo Amarelo (LA), Latossolo Amarelo plíntico, Latossolo Amarelo petroplíntico (concrecionário) e Plintossolo Háplico, todos muito argilosos, com teores de Fe2O3 e TiO2 relativamente homogêneos e índices Ki e Kr indicativos de mineralogia oxídica. Na segunda superfície, os solos apresentam maior variação quanto à textura e teores de Fe e Ti. Predominam LV e LV acriférrico, além de LVA e LA. Nos limites com as chapadas, observa-se a ocorrência de LVA e LA acriférricos endopetroplínticos. Na terceira superfície, que disseca as anteriores, predominam solos menos intemperizados, com atributos muito variáveis, como Cambissolo Háplico, Argissolos Vermelho e Vermelho-Amarelo, Nitossolo Vermelho eutroférrico, Neossolo Litólico e Neossolo Flúvico. O trabalho inclui a proposição de um modelo de evolução para a paisagem regional.