Orbital-polarization terms: From a phenomenological to a first-principles description of orbital magnetism in density-functional theory

Phenomenological orbital-polarizition (OP) terms have been repeatedly introduced in the single-particle equations of spin-density-functional theory, in order to improve the description of orbital magnetic moments in systems containing transition metal ions. Here we show that these ad hoc corrections can be interpreted as approximations to the exchange-correlation vector potential A(xc) of current-density functional theory (CDFT). This connection provides additional information on both approaches: phenomenological OP terms are connected to first-principles theory, leading to a rationale for their empirical success and a reassessment of their limitations and the approximations made in their derivation. Conversely, the connection of OP terms with CDFT leads to a set of simple approximations to the CDFT potential A(xc), with a number of desirable features that are absent from electron-gas-based functionals. (C) 2008 Wiley Periodicals, Inc.

Detailed analysis of the charge transfer complex N,N-dimethylaniline-SO(2) by Raman spectroscopy and density functional theory calculations

Although the amine sulfur dioxide chemistry was well characterized in the past both experimentally and theoretically, no systematic Raman spectroscopic study describes the interaction between N,N-dimethylaniline (DMA) and sulfur dioxide (SO(2)). The formation of a deep red oil by the reaction of SO(2) with DMA is an evidence of the charge transfer (CT) nature of the DMA-SO(2) interaction. The DMA -SO(2) normal Raman spectrum shows the appearance of two intense bands at 1110 and 1151 cm(-1), which are enhanced when resonance is approached. These bands are assigned to nu(s)(SO(2)) and nu(phi-N) vibrational modes, respectively, confirming the interaction between SO(2) and the amine via the nitrogen atom. The dimethyl group steric effect favors the interaction of SO(2) with the ring pi electrons, which gives rise to a pi-pi* low-energy CT electronic transition, as confirmed by time-dependent density functional theory (TDDFT) calculations. In addition, the calculated Raman DMA-SO(2) spectrum at the B3LYP/6-311++g(3df,3pd) level shows good agreement with the experimental results (vibrational wavenumbers and relative intensities), allowing a complete assignment of the vibrational modes. A better understanding of the intermolecular interactions in this model system can be extremely useful in designing new materials to absorb, detect, or even quantify SO(2). Copyright (C) 2009 John Wiley & Sons, Ltd.

FT-Raman, FTIR and density functional theory studies of a hydrogen-bonded formamide: pyridine complex

Raman and IR experiments have been carried out on formamide (FA) and pyridine (Py) mixtures at different compositions. The appearance of a new Raman band at 996 cm(-1) (nu(1) region of Py), whose intensity depends on the FA concentration, is assigned to an FA: Py adduct and this result is in excellent agreement with those of other authors who employed noisy light-based coherent Raman scattering spectroscopy (I((2)) CARS). Another band at 1587 cm(-1) (nu(8) region of Py) has been observed for the first time by using Raman and IR spectroscopies. Its intensity shows the same dependence on the FA concentration and this fact allows us to also attribute it to an FA: Py adduct. The good relationship between the Raman and IR data demonstrates the potential of the vibrational spectroscopy for this kind of study. Owing to higher absolute Raman scattering cross section, the nu(1) region of Py has been chosen for the quantitative analysis and a stoichiometry of 1 : 1 FA: Py is reported. The experimental data are very well supported by the density functional theory (OFT) calculation, which was employed for the first time to the present system. Furthermore, the actual investigation shows an excellent agreement with those reported from computational calculations for similar systems. A comparison with our previous studies confirms that: the solvent dielectric constant determines the stoichiometry of a given Lewis acid-base adduct in the infinite dilution limit. Copyright (C) 2009 John Wiley & Sons, Ltd.

Axial ligand influence on geometries, charge distributions and electronic structures of iron tetraazamacrocycle [Fe((II))TIM(X)(Y)](2+) complexes assessed by Density Functional Theory

We employed the Density Functional Theory along with small basis sets, B3LYP/LANL2DZ, for the study of FeTIM complexes with different pairs of axial ligands (CO, H(2)O, NH(3), imidazole and CH(3)CN). These calculations did not result in relevant changes of molecular quantities as bond lengths, vibrational frequencies and electronic populations supporting any significant back-donation to the carbonyl or acetonitrile axial ligands. Moreover, a back-donation mechanism to the macrocycle cannot be used to explain the observed changes in molecular properties along these complexes with CO or CH(3)CN. This work also indicates that complexes with CO show smaller binding energies and are less stable than complexes with CH(3)CN. Further, the electronic band with the largest intensity in the visible region (or close to this region) is associated to the transition from an occupied 3d orbital on iron to an empty pi* orbital located at the macrocycle. The energy of this Metal-to-Ligand Charge Transfer (MLCT) transition shows a linear relation to the total charge of the macrocycle in these complexes as given by Mulliken or Natural Population Analysis (NPA) formalisms. Finally, the macrocycle total charge seems to be influenced by the field induced by the axial ligands. (C) 2011 Elsevier Ltd. All rights reserved.

"Eu pensei que ia sair daqui falando inglês": um estudo sistêmico-funcional sobre papéis sociais atribuídos por alunos de um curso de Letras/Inglês

Research in the area of teacher training in English as a Foreign Language (CELANI, 2003, 2004, 2010; PAIVA, 2000, 2003, 2005; VIEIRA-ABRAHÃO, 2010) articulates the complexity of beginning teachers classroom contexts aligned with teaching language as a social and professional practice of the teacher in training. To better understand this relationship, the present study is based on a corpus of transcribed interviews and questionnaires applied to 28 undergraduate students majoring in Letters/English emphasis, at a public university located in the interior of the Western Amazon region, soliciting their opinions about the reforms made in the curriculum of this Major. Interviews and questionnaires were used as data collection instruments to trace a profile of the students organized in Group 1, with freshmen and sophomore undergraduates who are following the 2009 curriculum, and Group 2, with junior and senior undergraduates who are following the 2006 curriculum. The objectives are to identify, to characterize and to analyze the types of pronouns, roles and social actors represented in the opinions of these students in relation to their teacher training curriculum. The theoretical support focuses on the challenge of historical and contemporary routes from English teachers initial education programs (MAGALHÃES; LIBERALLI, 2009; PAVAN; SILVA, 2010; ALVAREZ, 2010; VIANA, 2011; PAVAN, 2012). Our theoretical perspective is based on the Systemic Functional Grammar of Halliday (1994), Halliday and Hasan (1989), Halliday and Matthiessen (2004), Eggins (1994; 2004) and Thompson (2004). We focus on the concept of the Interpersonal meaning, specifically regarding the roles articulated in the studies by Delu (1991), Thompson and Thetela (1995), and in the Portuguese language such as Ramos (1997), Silva (2006) and Cabral (2009). Moreover, we ascribe van Leeuwen s (1997; 2003) theory of Representation of Social Actors as a theoretical framework in order to identify the sociological aspect of social actors represented in the students discourse. Within this scenario, the analysis unfolds on three levels: grammatical (pronouns), semantic (roles), and discursive (social actors). For the analysis of interpersonal realizations present in the students opinions, we use the computational program WordSmith Tools (SCOTT, 2010) and its applications Wordlist and Concord to quantify the occurrences of the pronouns I, You and They, which characterize the roles and social actors of the corpus. The results show that the students assigned the following roles to themselves: (i) apprentice to express their initial process of English language learning; (ii) freshman to reveal their choice of Major in Letters/English emphasis; (iii) future teacher to relate their expectations towards a practicing professional. To assign the roles to professors in the major, the students used the metaphor of modality (I think) to indicate the relationship of teacher training, while they are in the role of a student and as a future teacher. From these evidences the representation of the students as social actors emerges in roles such as: (i) active roles; (ii) passive roles and (iii) personalized roles. The social actors represented in the opinions of the students reflect the inclusion of these roles assigned to the actions expressed about their experiences and expectations derived from their teacher training classroom

Sujeitos e atores sociais nas representações discursivas de docentes da rede estadual de ensino em Sergipe: uma análise crítica em tempos de Ideb

According to the studies in Applied Linguistics, this thesis is based on an interdisciplinary perspective (Critical Discourse Analysis, Sociology towards Social Change, Cultural Studies and Systemic-Functional Linguistics). The overall objective of the research was to analyze the discourses of Elementary School teachers in the state of Sergipe, by means of the discursive representations of the social actors, the processes of subjectivity and their fragmented identities in the context of standardized evaluations before the requirements of globalized pedagogical practices, based on the result-based management. The critical analysis of such discourses was motivated by the rapid pace with which the demands of innovation become part of the classroom, aiming at reaching the target in what concerns the indexes of the rankings which characterize the globalized discourse of the national education management, like Ideb (Basic Education Development Index), which makes teachers change their discourses, become silent or keep resistant. The work was initially endorsed by the theoretical lines of the Critical Discourse Analysis (FAIRCLOUGH, 2001, 2006), and poses a proposal for such purpose: the ASCD Discourse Sociological and Communicative Approach (PEDROSA, 2012, 2013). This is an interpretative-qualitative study of the Critical Discourse Analysis (FAIRCLOUGH, 2001, 2003; RAMALHO ; RESENDE, 2011) and to carry it out, semi-structured interviews were used as instruments of data generation (BAUER; GASKELL, 2011; GILL, 2011). Its corpus is composed of thirteen accounts of teachers from the Elementary school who teach Portuguese and work in the fifteen schools which were chosen to be the universe of the research at the Regional Board of Education (02) in the state of Sergipe. Such narratives are related to their impressions, expectations and actions which favor the management of results to which they have to submit themselves. The analytical overview of sociological and discursive line comes from the pan-semiotic categories (Inclusion and Exclusion) which appear in the theory of Representation of Social Actors (VAN LEEUWEN, 1997, 2008). To present the processes of subjectivity of these teachers, this work is based on the socio-analytical proposal of the classification of the subjects, which stems from the individual s work in the Gestão Relacional de Si , which comes from the Applied Sociology (towards) Social Change (BAJOIT, 2006, 2009). The discursive analyses were guided word for word, in their majority, by having the Systemic Functional Grammar as their theoretical basis, specifically by the processes of the Transitivity System postulated by Halliday, (1985); Halliday and Mathiessen, (2004); Eggins (2004); Cunha and Souza (2011). The work makes the field of Cultural Studies emerge towards the dialogue and the presentation of the fragmented identities of the teachers in the context of late modernity (GIDDENS, 2002; HALL, 2011). The thesis promoted a reflection over the teacher s condition, who is immerse in this context of knowledge construction of the present Brazilian educational system, the standardized evaluations, the indexes of development, the targets and the rankings. The considerations and outcomes of such a research dealt with the teachers emerging social practices and the need of planned initial and continuing teacher education towards the new moment which is foreseeable

Density functional theory study on the structural and electronic properties of low index rutile surfaces for TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 composite systems

The present study is concerned with the structural and electronic properties of the TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 composite systems. Periodic quantum mechanical method with density functional theory at the B3LYP level has been carried out. Relaxed surface energies, structural characteristics and electronic properties of the (I 10), (0 10), (10 1) and (00) low-index rutile surfaces for TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 models are studied. For, comparison purposes, the bare rutile TiO2 and SnO2 structures are also analyzed and compared with previous theoretical and experimental data. The calculated surface energy for both rutile TiO2 and SnO2 surfaces follows the sequence (110) < (010) < (101) < (001) and the energy increases as (010) < (101) < (110) < (001) and (010) approximate to (110) < (101) < (001) for SnO2/TiO2/SnO2 and TiO2/SnO2/TiO2 composite systems, respectively. SnO2/TiO2/SnO2 presents larger values of surface energy than the individual SnO2 and TiO2 metal oxides and the TiO2/SnO2/TiO2 system renders surface energy values of the same order that the TiO2 and lower than the SnO2. An analysis of the electronic structure of the TiO2/SnO2/TiO2 and SnO2/TiO2/SnO2 systems shows that the main characteristics of the upper part of the valence bands for all the studied surfaces are dominated by the external layers, i.e., by the TiO2 and the SnO2, respectively, and the topology of the lower part of the conduction bands looks like the core layers. There is an energy stabilization of both valence band top and conduction band bottom for (110) and (010) surfaces of the SnO2/TiO2/SnO2 composite system in relation to their core TiO2, whereas an opposite trend is found for the same surfaces of the TiO2/SnO2/TiO2 composite system in relation to the bare SnO2. The present theoretical results may explain the growth of TiO2@SnO2 bimorph composite nanotape.

Intercalation processes and diffusion paths of lithium ions in spinel-type structured Li(1+x)Ti(2)O(4): Density functional theory study

Intercalation processes and corresponding diffusion paths of Li ions into spinel-type structured Li(1+x)Ti(2)O(4) (0 <= x <= 0.375) are systematically studied by means of periodic density functional theory calculations for different compositions and arrangements. An analysis of the site preference for intercalation processes is carried out, while energy barriers for the diffusion paths have been computed in detail. Our results indicate that the Li insertion is thermodynamically favorable at octahedral sites 16c in the studied composition range, and Li migration from tetrahedral sites 8a to octahedral sites 16c stabilizes the structure and becomes favorable for compositions x >= 0.25. Diffusion paths from less stable arrangements involving Li migrations between tetrahedral and octahedral sites exhibit the lowest energy barrier since the corresponding trajectories and energy profiles take place across a triangle made by three neighboring oxygen anions without structural modification. Theoretical and experimental diffusion coefficients are in reasonable agreement.

Density functional theory calculation of the electronic structure of Ba0.5Sr0.5TiO3: Photoluminescent properties and structural disorder

First-principles quantum-mechanical techniques, based on density functional theory (B3LYP level) were employed to study the electronic structure of ordered and deformed asymmetric models for Ba0.5Sr 0.5TiO3. Electronic properties are analyzed and the relevance of the present theoretical and experimental results on the photoluminescence behavior is discussed. The presence of localized electronic levels in the band gap, due to the symmetry break, would be responsible for the visible photoluminescence of the amorphous state at room temperature. Thin films were synthesized following a soft chemical processing. Their structure was confirmed by x-ray data and the corresponding photoluminescence properties measured.

Gramaticalização e (inter)subjetivização na modalização em português: um estudo de pode ser

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Release of Cyanopyridine from a Ruthenium Complex Adsorbed on Gold: Surface-Enhanced Raman Scattering, Electrochemistry, and Density Functional Theory Analyses

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

TinO2n-1 Magneli phases studied using density functional theory

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Capacitance spectroscopy and density functional theory

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Interactions between 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid and gamma-Al2O3 (100) surface calculated by density functional theory

The main aim of this work is to investigate the 1-butyl-3-methylimidazolium tetrafluoroborate ([C4C1Im]+[BF4]-) ionic liquid (IL) adsorption on the gamma-Al2O3 (100) by density functional theory calculations to try to rationalize the adsorption as an electrostatic phenomenon. Optimized geometries and interaction energies of IL one-monolayer on the gamma-Al2O3 were obtained on high surface coverage (one cationanion pair per 94.96 nm2). A study of dispersion force was made to estimate its contribution to the adsorption. Overall, the process is ruled by electrostatic interaction between ions and surface. Adsorption of the anion [BF4]- and cation [C4C1Im]+ was also studied by Bader charge analysis and charge density difference for supported and unsupported situations. It is suggested that the IL ions have their charges maintained with significant anion cloud polarization inward to the acid aluminum sites. (c) 2012 Wiley Periodicals, Inc.

Encapsulation of small magnetic clusters in fullerene cages: A density functional theory investigation within van der Waals corrections

The encapsulation of magnetic transition-metal (TM) clusters inside carbon cages (fullerenes, nanotubes) has been of great interest due to the wide range of applications, which spread from medical sensors in magnetic resonance imaging to photonic crystals. Several theoretical studies have been reported; however, our atomistic understanding of the physical properties of encapsulated magnetic TM 3d clusters is far from satisfactory. In this work, we will report general trends, derived from density functional theory within the generalized gradient approximation proposed by Perdew, Burke, and Ernzerhof (PBE), for the encapsulation properties of the TMm@C-n (TM = Fe, Co, Ni; m = 2-6, n = 60,70,80,90) systems. Furthermore, to understand the role of the van der Waals corrections to the physical properties, we employed the empirical Grimme's correction (PBE + D2). We found that both PBE and PBE + D2 functionals yield almost the same geometric parameters, magnetic and electronic properties, however, PBE + D2 strongly enhances the encapsulation energy. We found that the center of mass of the TMm clusters is displaced towards the inside C-n surfaces, except for large TMm clusters (m = 5 and 6). For few cases, e. g., Co-4 and Fe-4, the encapsulation changes the putative lowest-energy structure compared to the isolated TMm clusters. We identified few physical parameters that play an important role in the sign and magnitude of the encapsulation energy, namely, cluster size, fullerene equatorial diameter, shape, curvature of the inside C-n surface, number of TM atoms that bind directly to the inside C-n surface, and the van der Waals correction. The total magnetic moment of encapsulated TMm clusters decreases compared with the isolated TMm clusters, which is expected due to the hybridization of the d-p states, and strongly depends on the size and shape of the fullerene cages.