Variational Monte Carlo study of core-valence separation schemes for first-row atoms and positive ions /

All-electron partitioning of wave functions into products ^core^vai of core and valence parts in orbital space results in the loss of core-valence antisymmetry, uncorrelation of motion of core and valence electrons, and core-valence overlap. These effects are studied with the variational Monte Carlo method using appropriately designed wave functions for the first-row atoms and positive ions. It is shown that the loss of antisymmetry with respect to interchange of core and valence electrons is a dominant effect which increases rapidly through the row, while the effect of core-valence uncorrelation is generally smaller. Orthogonality of the core and valence parts partially substitutes the exclusion principle and is absolutely necessary for meaningful calculations with partitioned wave functions. Core-valence overlap may lead to nonsensical values of the total energy. It has been found that even relatively crude core-valence partitioned wave functions generally can estimate ionization potentials with better accuracy than that of the traditional, non-partitioned ones, provided that they achieve maximum separation (independence) of core and valence shells accompanied by high internal flexibility of ^core and Wvai- Our best core-valence partitioned wave function of that kind estimates the IP's with an accuracy comparable to the most accurate theoretical determinations in the literature.

Generating finite integral relation algebras

Relation algebras and categories of relations in particular have proven to be extremely useful as a fundamental tool in mathematics and computer science. Since relation algebras are Boolean algebras with some well-behaved operations, every such algebra provides an atom structure, i.e., a relational structure on its set of atoms. In the case of complete and atomic structure (e.g. finite algebras), the original algebra can be recovered from its atom structure by using the complex algebra construction. This gives a representation of relation algebras as the complex algebra of a certain relational structure. This property is of particular interest because storing the atom structure requires less space than the entire algebra. In this thesis I want to introduce and implement three structures representing atom structures of integral heterogeneous relation algebras, i.e., categorical versions of relation algebras. The first structure will simply embed a homogeneous atom structure of a relation algebra into the heterogeneous context. The second structure is obtained by splitting all symmetric idempotent relations. This new algebra is in almost all cases an heterogeneous structure having more objects than the original one. Finally, I will define two different union operations to combine two algebras into a single one.

Selected configuration interaction with truncation energy error and application to the Ne atom

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 BK 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, ΔEK=(E-HKK)BK2/(1-BK2), with BK determined from coefficients of singly and doubly excited configurations. The truncation energy error from disconnected configurations, Δdis, is approximated by the sum of ΔEKS 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 ES is computed by CI in a selected space S, and EM=E S+ΔEdis+δE, where δE 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× 109 CSFs (1.1 × 1012 determinants) containing up to quadruply excited CSFs. Accurate energy contributions of quintuples and sextuples in a model space of 6.5 × 1012 CSFs are obtained. The impact of SCI on various orbital methods is discussed. Since ΔEdis 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 ES is taken up in a companion paper

Monitoring one-electron photo-oxidation of guanine in DNA crystals using ultrafast infrared spectroscopy

To understand the molecular origins of diseases caused by ultraviolet and visible light, and also to develop photodynamic therapy, it is important to resolve the mechanism of photoinduced DNA damage. Damage to DNA bound to a photosensitizer molecule frequently proceeds by one-electron photo-oxidation of guanine, but the precise dynamics of this process are sensitive to the location and the orientation of the photosensitizer, which are very difficult to define in solution. To overcome this, ultrafast time-resolved infrared (TRIR) spectroscopy was performed on photoexcited ruthenium polypyridyl–DNA crystals, the atomic structure of which was determined by X-ray crystallography. By combining the X-ray and TRIR data we are able to define both the geometry of the reaction site and the rates of individual steps in a reversible photoinduced electron-transfer process. This allows us to propose an individual guanine as the reaction site and, intriguingly, reveals that the dynamics in the crystal state are quite similar to those observed in the solvent medium.

A Morphological View of the Sodium 4,4 `-Distyrylbiphenyl Sulfonate Fluorescent Brightness Distribution on Regenerated Cellulose Fibers

Evidence of the sorption of the whitening agent sodium 4,4`-distyrylbiphenyl sulfonate in the presence of the anionic surfactant sodium dodecylsulfate or the cationic surfactant dodecyl trimethyl ammonium chloride on regenerated cellulose fibers is given by several microscopy techniques. Scanning electron microscopy provided images of the cylindrical fibers with dimensions of 3.5 cm (length) and 13.3 mu m (thickness), with empty cores of 1 mu m diameter and a smooth surface. Atomic force microscopy showed a fiber surface with disoriented nanometric domains using both tapping-mode height and phase image modes. Atomic force microscopy also showed that the whitening agent and surfactant molecules were sorbed onto the fiber surface, in agreement with the adsolubilization sorption model. Transmission electron microscopy showed fibers with nanometric parallel cylinders, surrounded by holes where the fluorescent whitening molecules accumulated. On the basis of these techniques, we conclude that the sorption process occurs preferentially on the fiber surface in contact with the water solution, and under saturated conditions, the whitening agent penetrates into the pores and are simultaneously sorbed on the pore walls bulk, forming molecular aggregates. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 2321-2327, 2010

Structural-electronic aspects related to the near-infrared light emission of Fe-doped silicon films

The need of efficient (fast and low consumption) optoelectronic devices has always been the driving force behind the investigation of materials with new or improved properties. To be commercially attractive, however, these materials should be compatible with our current micro-electronics industry and/or telecommunications system. Silicon-based compounds, with their matured processing technology and natural abundance, partially comply with such requirements-as long as they emit light. Motivated by these issues, this work reports on the optical properties of amorphous Si films doped with Fe. The films were prepared by sputtering a Si+Fe target and were investigated by different spectroscopic techniques. According to the experimental results, both the Fe concentration and the thermal annealing of the samples induce changes in their atomic structure and optical-electronic properties. In fact, after thermal annealing at similar to 750 degrees C, the samples partially crystallize with the development of Si and/or beta-FeSi(2) crystallites. In such a case, certain samples present light emission at similar to 1500 nm that depends on the presence of beta-FeSi(2) crystallites and is very sensitive to the annealing conditions. The most likely reasons for the light emission (or absence of it) in the considered Fe-doped Si samples are presented and discussed in view of their main structural-electronic characteristics. (C) 2011 Elsevier Ltd. All rights reserved.

Análise das avaliações realizadas na disciplina de arquitetura atômica e molecular no curso de química, modalidade a distância da UFRN

The field of education is very rich and allows us to research in various aspects. The area of chemical education has been growing more and more, and an important aspect that has been researching this area is about the learning difficulties of students. The approach of the themes atomic structure and chemical bonds are developed in high school and have many problems that are often brought to higher education becoming an obstacle to the advancement of learning. It is necessary for these initial themes - the atomic structure and chemical bonds - are well understood by the student to the other contents of Chemistry will be understood more easily. This paper aims to describe, analyze errors and difficulties presented in the assessments of the discipline Atomic and Molecular Architecture, the students of the degree course in Chemistry - EAD, with respect to the contents of " Atomic Structure and Chemical Bonding ", by of the assessments made by the students and the Virtual Learning Environment (VLE), taking into account the activities , discussion forum and access to materials . AVA allows obtaining reports which were used to analyze regarding access / participation to assess their contribution to learning and its relation to the final result (pass / fail). It was observed that the most frequent errors in the assessments are related to the early part of the chemistry that is the understanding of atomic structure and evolution models. Students who accessed the extra material and participated in the activities and forums were students who achieved success in the course. Ie, the difficulties were emerging and the use of available teaching strategies, students could minimize such difficulties, making their performance in activities and assessments were better. Was also observed by attending the AVA, the discipline began with a large withdrawal from the page access as well as the frequency of face- evidence from observation in Listing presence of classroom assessments

Structural characteristics of silica sonogels prepared with different proportions of TEOS and TMOS

Sonohydrolysis of mixtures of tetraethoxysilane (TEOS) and tetramethoxysilane (TMOS) with different TMOS/(TMOS + TEOS) molar ratio R was carried out to obtain similar to 2.0 x 10(-3) mol SiO2/cm(3) and similar to 86%-volume liquid phase wet gels. Aerogels were obtained by supercritical CO2 extraction in autoclave. The samples were analyzed by small-angle X-ray scattering (SAXS) and nitrogen adsorption. The structure of the wet gels can be described as a mass fractal structure with fractal dimension D similar to 2.2 and characteristic length increasing from similar to 4.6 nm for pure TEOS to similar to 6.4 nm for pure TMOS. A fraction of the porosity is eliminated with the supercritical process. The fundamental role of the TMOS/(TMOS + TEOS) molar ratio on the structure of the aerogels is to increase the porosity and the pore mean size as R changes from pure TEOS to pure TMOS. The supercritical process increases the mass fractal dimension and shortens the fractality domain in the mesopore region. A secondary structure appearing in the micropore region of the aerogels can be described as a mass/surface fractal structure with correlated mass fractal dimension D-m similar to 2.6 and surface fractal dimension D-s similar to 2.3. (C) 2007 Elsevier B.V. All rights reserved.

Photoluminescence at room temperature in amorphous SrTiO3 thin films obtained by chemical solution deposition

Intense photoluminescence in highly disordered strontium titanate amorphous thin films prepared by the polymeric precursor method was observed at room temperature (300 K). The luminescence spectra of SrTiO3 amorphous thin films at room temperature revealed an intense single-emission band in the visible region. X-ray absorption near edge structure was used to probe the local atomic structure of SrTiO3 amorphous and crystalline thin films. Photoluminescence intensity in the 535 nm range was found to be correlated with the presence of non-bridging oxygen defects. A discussion is presented of the nature of this photoluminescence, which may be related to the disordered structure in SrTiO3 amorphous thin films. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Structural evolution of aerogels prepared from TEOS sono-hydrolysis upon heat treatment up to 1100 degrees C

The structural evolution of aerogels prepared from TEOS sono-hydrolysis was studied as a function of the temperature of heat treatment up to 1100 degreesC by means of small angle X-ray scattering (SAXS) and density measurements. The mass fractal structure of the original wet sonogel (with scattering exponent alpha similar to 2.2) apparently transforms to a surface fractal structure in a length scale lesser than similar to1.5 nm, upon the process resulting in aerogel. Such a structural transformation is interpreted by the formation of new particles with characteristic dimension of similar to1.5 nm, with rough boundaries or electronic density fluctuations (or ultra-micropores) in their interior. The structural arrangement of these particles seem to preserve part of mass fractal characteristics of the original wet sonogel, now in a length scale greater than similar to1.5 nm. The electronic density heterogeneities in the particles start to be eliminated at around 800 degreesC and, at 900 degreesC, the particles become perfectly homogeneous, so the structure can be described as a porous structure with a porosity of similar to68% with similar to9.0 nm mean size pores and similar to4.3 nm mean size solid particles. Above 900 degreesC, a vigorous viscous flux sintering process sets in, eliminating most of the porosity and increasing rapidly the bulk density in an aerogel-glass transformation. (C) 2003 Elsevier B.V. All rights reserved.

A SAXS study of the nanostructural characteristics of TEOS-derived sonogels upon heat treatment up to 1100 degrees C

Xerogels obtained from the acid-catalyzed and ultrasound stimulated hydrolysis of TEOS were submitted to heat treatment at temperatures ranging from 60 to 1100 degreesC and studied by small-angle X-ray scattering (SAXS). The SAXS intensity as a function of the modulus of the scattering vector q was obtained in the range from q(0) = 0.19 to q(m) = 4.4 nm(-1). At 60 degreesC the xerogels exhibit an apparent surface fractal structure with a fractal dimension D-s similar to 2.5 in a length scale ranging from 1/q(1) similar to 1 to 1/q(m) similar to 0.22 nm. This structure becomes extremely rough at 120 degreesC (D-s similar to 3) and at 150 degreesC, it apparently converts to a mass fractal with a fractal dimension D similar to 2.4. This may mean an emptying of the pores with preservation of a share of the original mass fractal structure of the wet aged gel, for it had presented a mass fractal dimension D similar to 2.2. A well characterized porous structure formed by 2.0 nm mean size pores with smooth surface of about 380 m(2)/g is formed at 300 degreesC and remains stable until approximately 800 degreesC. At 900 degreesC the SAXS intensity vanishes indicating the disappearance of the pores in the probed length scale. The elimination of the nanopores occurs by a mechanism in which the number of pores diminishes keeping constant their mean size. The xerogels exhibit a foaming phenomenon above 900 degreesC and scatter following Porod's law as does a surface formed by a coarse structure. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Structural characteristics of silica sonogels prepared with additions of isopropyl alcohol

Wet silica gels with similar to 1.4 x 10(-3) mol SiO2/cm(3) and similar to 92 vol% liquid phase were obtained from sonohydrolysis of tetraethoxysilane (TEOS) with different additions of isopropyl alcohol ( IPA). The IPA/TEOS molar ratio R was changed from 0 to 4. Aerogels were obtained by supercritical CO2 extraction. The samples were analyzed by small-angle X-ray scattering (SAXS) and nitrogen adsorption. The wet gels exhibit mass fractal structure with fractal dimension increasing from D similar to 2.10 to D similar to 2.22, characteristic length xi decreasing from similar to 9.5 to similar to 6.9 nm, as R increases from 0 to 4, and an estimated characteristic length for the primary silica particles lower than similar to 0.3 nm. The supercritical process apparently eliminates a fraction of the porosity, increasing the mass fractal dimension and shortening the fractality domain in the mesopore region. The fundamental role of isopropyl alcohol on the structure of the resulting aerogels is to decrease the porosity and the pore mean size as R changes from pure TEOS to R = 4. A secondary structure appearing in the micropore region of the aerogels can be described as a mass/surface fractal structure, with correlated mass fractal dimension D-m similar to 2.7 and surface fractal dimension D-s similar to 2.3, as inferred from SAXS and nitrogen adsorption data.

Coordination of Eu3+ ions in siliceous nanohybrids containing short polyether chains and bridging urea cross-links

Infrared and photoluminescence spectroscopies have been used to investigate the local environment of the Eu3+ ions in luminescent sol-gel derived materials-di-ureasils-based on a hybrid framework represented by U(600). This host is composed of a siliceous backbone grafted, through urea cross-links, to both ends of polymer segments incorporating 8.5 oxyethylene repeat units. The active centers have been introduced as europium perchlorate, Eu(ClO4)3. Samples with compositions n = 232, 62, 23, 12, and 6 (where n denotes the ratio of (OCH2CH2) moieties per lanthanide ion) have been examined. The combination of the information retrieved from the analysis of characteristic bands of the FTIR spectra-the perchlorate and the Amide I/Amide II features-with that obtained from the photoluminescence data demonstrates that at compositions n = 232 and 62 the anions are free, whereas the Eu3+ ions are complexed by the heteroatoms of the polyether chains. At higher salt concentration, the cations are bonded, not only to the ClO4 - ions, but also to the ether oxygen atoms of the organic segments and to the carbonyl oxygen atoms of the urea linkages. The dual behavior of U(600) with respect to cation coordination has been attributed to the presence in this nanohybrid of strong hydrogen-bonded urea-urea structures, which, at low salt content, cannot be disrupted, thus inhibiting the formation of Eu3+-O=C(urea) contacts and promoting the interaction between the lanthanide ions and the (OCH2CH2) moieties. The present work substantiates the claim that the activation of the coordinating sites of the di-ureasil framework can be tuned by varying either the guest salt concentration at constant chain length or the length of the.organic segments at constant salt concentration. This relevant property opens challenging new prospects in the fields of application of this class of hybrids. © 2001 American Chemical Society.

Influence of oxygen flow on crystallization and morphology of LiNbO 3 thin films

Polymeric precursor solution (Pechini method) was used to deposit LiNbO 3 thin films by spin-coating on (100) silicon substrates. X-ray diffraction data of thin films showed that the increase of oxygen flow promotes a preferred orientation of (001) LiNbO 3 planes parallel to the substrate surface. Surface roughness and grain size, observed by atomic force microscopy, change also with oxygen flow. © 2002 Taylor & Francis.

The two-impurity Anderson model: An effective medium approach

The two-impurity Anderson model is solved within a effective medium approach. All impurity parameters are modelled via Slater atomic orbitals. Impurity spectral densities and spin correlation functions are readily computed. Results are presented for the zero temperature, half-filled case. © 2002 Elsevier Science B.V. All rights reserved.