First order reversal curve analysis of nanocrystalline Pd80Co20 alloy films

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

Rational approximations of the Arrhenius integral using Jacobi fractions and gaussian quadrature

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

Peak Separation by Derivative Spectroscopy Applied to FTIR Analysis of Hydrolized Silica

Reliable spectral analysis is only achieved if the spectrum is thoroughly investigated in regard to all hidden and overlapped peaks. This paper describes the steps undertaken to find and separate such peaks in the range of 3000 to 4000 cm(-1) in the case of three different infrared absorption spectra of the glass surface of hydrolyzed silica optical fibers. Peak finding was done by the analysis of the second and fourth derivatives of the digital data, coupled with the available knowledge of infrared spectroscopy of silica-water interaction in the investigated range. Peak separation was accomplished by curve fitting with four different models. The model with the best fit was described by a sum of pure Gaussian peaks. Shoulder limit and detection limit maps were used to validate the revealed spectral features.

Limit between stages I and II of a seed imbibition curve

O conhecimento das fases de absorção de água das diferentes espécies é importante em pesquisas objetivando melhorar a qualidade das sementes, utilizando tratamentos como condicionamento osmótico, pré-hidratação e uso de bioreguladores. O objetivo do presente trabalho foi estabelecer uma metodologia para determinar o limite entre a primeira e a segunda fase do processo, considerando o modelo W = f(t) - (a - w0)exp(-kt), utilizando testes estatísticos. O limite entre as duas primeiras fases do processo de absorção de água pelas sementes, foi determinado utilizando-se a distribuição assintótica de uma função de estimadores. O ponto a partir do qual esta diferença (W*) deixa de ser significativa foi determinado utilizando-se o teste estatístico T de Student. Para os dados utilizados como exemplo, tem-se o modelo ou =(0,434 + 0,00162 t) - (0,434 - w o)exp(-0,121 t), com r² = 0,98 e W* = (0,434 - w o) exp(-0,121 t). O valor de t encontrado (27,2 horas) é menor do que o valor determinado, considerando-se como critério para mudança de fase a diferença de 1% entre a assíntota e o valor estimado pelo modelo ajustado. Essa diferença de duas horas corresponde a 0,28% de água absorvida.

Study on the orientation degree of Pb1-xLaxTiO3 thin films by the rocking curve technique and its morphological aspects

Thin films of perovskite-type materials such as PbTiO3, BaTiO3, (Pb,La)TiO3, (Pb, La)(ZrTi)O-3, KNbO3, and Pb(Mg,Nb)03 have been attracting great interest for applications like non-volatile memories, ultrasonic sensors and optical devices. Thin film should be epitaxially grown or at least highly textured since the properties of this anisotropic material depend on the crystallographic orientation. For optical devices, in particular, an epitaxial thin film without defects are essential to reduce optical propagation losses. Pb1-xLaxTiO3 (PLT) where x=0, 13 and 27% thin films were prepared by a chemical method (polymeric precursors method), and deposited by the spin coating technique onto substrates of SrTiO3 (STO) and LaAlO3 (LAO). The films were then beat treated at 500 degrees C in a controlled atmosphere of 0,. The orientation degree of the thin films was obtained from rocking curve technique, by means of X-ray difftaction analysis. A microstructural study revealed that the films were crack-free, homogeneous and have low roughness. (c) 2006 Elsevier B.V. All rights reserved.

Gaussian basis sets to the theoretical study of the electronic structure of perovskite (LaMnO3)

The Generator Coordinate Hartree-Fock (GCHF) method is applied to generate extended (20s14p), (30s19p13d), and (31s23p18d) Gaussian basis sets for the 0, Mn, and La atoms, respectively. The role of the weight functions (WFs) in the assessment of the numerical integration range of the GCHF equations is shown. These basis sets are then contracted to [5s3p] and [11s6p6d] for 0 and Mn atoms, respectively, and [17s11p7d] for La atom by a standard procedure. For quality evaluation of contracted basis sets in molecular calculations, we have accomplished calculations of total and orbital energies in the Hartree-Fock-Roothaan (HFR) method for (MnO1+)-Mn-5 and (LaO1+)-La-1 fragments. The results obtained with the contracted basis sets are compared with values obtained with the extended basis sets. The addition of one d polarization function in the contracted basis set for 0 atom and its utilization with the contracted basis sets for Mn and La atoms leads to the calculations of dipole moment and total atomic charges of perovskite (LaMnO3). The calculations were performed at the HFR level with the crystal [LaMnO3](2) fragment in space group C-2v the values of dipole moment, total energy, and total atomic charges showed that it is reasonable to believe that LaMnO3 presents behaviour of piezoelectric material. (C) 2003 Elsevier B.V. All rights reserved.

The generator coordinate Hartree-Fock method as strategy for building Gaussian basis sets to ab initio study of the process of adsorption of sulfur on platinum (200) surface

The scheme named generator coordinate Hartree-Fock method (GCHF) is used to build (22s14p) and (33s22p16d9f) gaussian basis sets to S ((3)P) and Pt ((3)D) atoms, respectively. Theses basis sets are contracted to [13s10p] and [19s13p9d5f] through of Dunning's segmented contraction scheme and are enriched with d and g polarization functions, [13s10p1d] and [19s13p9d5flg]. Finally, the [19s13p9d5f1g] basis Set to Pt ((3)D) was supplemented with s and d diffuse functions, [20s13p10d5flg], and used in combination with [13s10p1d] to study the effects of adsorption of S ((3)D) atom on a pt ((3)D) atom belonged to infinite Pt (200) surface. Atom-atom overlap population, bond order, and infrared spectrum of [pt(_)S](2 -) were calculated properties and were carried out at Hartree-Fock-Roothaan level. The results indicate that the process of adsorption of S ((3)P) on pt ((3)D) in the infinite Pt (200) surface is mainly caused by a strong contribution of sigma between the 3p(z) orbital of S ((3)P) and the 6s orbital of pt ((3)D). (c) 2004 Elsevier B.V. All rights reserved.

Design of Gaussian basis sets to the theoretical interpretation of IR-spectrum of hexaaquachromium (III) ion, tetraoxochromium (IV) ion, and tetraoxochromium (VI) ion

The Generator Coordinate Hartree-Fock (GCHF) method is employed to design 16s, 16s10p, 24s17p13d, 25s17p13d, and 26s17p Gaussian basis sets for the H ((2)S), O ((3)P), O(2-) ((1)S), Cr(3+) ((4)F), Cr(4+) ((3)F), and Cr(6+) ((1)S) atomic species. These basis sets are then contracted to (4s) for H ((2)S), (6s4p) for O ((3)P), and O(2-) ((1)S), (986p3d) for Cr(3+) ((4)F), (10s8p3d) for Cr(4+) ((3)F), and (13s7p) for Cr(6+) (1S) by a standard procedure. For evaluation of the quality of those basis sets in molecular calculations, we have accomplished studies of total and orbital (HOMO and HOMO-1) energies at the HF-Roothaan level for the molecular species of our interest. The results obtained with the contracted basis sets are compared to the values obtained with our extended basis sets and to the standard 6-311G basis set from literature. Finally, the contracted basis sets are enriched with polarization function and then utilized in the theoretical interpretation of IR-spectrum of hexaaquachromium (III) ion, [Cr(H(2)O)(6)](3+), tetraoxochromium (IV) ion, [CrO(4)](4-), and tetraoxochromium (VI) ion, [CrO(4)](2-). The respective theoretical harmonic frequencies and IR-intensities were computed at the density functional theory (DFT) level. In the DFT calculations we employed the Becke's 1988 functional using the LYP correlation functional. The comparison between the results obtained and the corresponding experimental values indicates a very good description of the IR-spectra of the molecular ions studied, and that the GCHF method is still a legitimate alternative for selection of Gaussian basis sets. (C) 2003 Elsevier B.V. All rights reserved.

The caprine oxyhemoglobin dissociation curve

The caprine oxyhemoglobin dissociation curve has not been previously defined. Blood from 10 healthy goats was equilibrated in a tonometer with calibrated gas mixtures of oxygen at concentrations of 95%, 21%, 13%, 12%, 10%, 9%, 8%, 5%, 4% and 2.5%, 5% carbon dioxide, balance nitrogen. The pH, partial pressure of oxygen (PO2), partial pressure of carbon dioxide (PCO2), total hemoglobin, oxyhemoglobin saturation, carboxyhemoglobin, methemoglobin, and oxygen content were measured. The PO2/oxyhemoglobin and the PO2/oxygen content relationships were graphed with curve-fitting software and a formula for calculating oxyhemoglobin from PO2 was generated. The maximum oxygen content per gram of hemoglobin was 1.29 ml of oxygen per gram of hemoglobin. The PO2 at which hemoglobin was 50% saturated (P-50) from the PO2/oxyhemoglobin relationship was 28.6 +/- 1.5 mmHg and that from the PO2/oxygen content relationships was 29.1 +/- 1.6 mmHg. The Hill coefficient for the PO2/oxyhemoglobin data was 3.0 +/- 0.4. (c) 2005 Elsevier Ltd. All rights reserved.

Designing Gaussian basis sets to the theoretical study of the piezoelectric effect of perovskite (BaTiO3)

Gaussian basis sets (24s14p, 30s19p14d, and 33s21p14d for O (P-3), Ti (S-5), and Ba (S-1) atoms, respectively), are designed with the strategy of the Generator Coordinate Hartree-Fock method. The basis sets are then contracted to [6s4p], [10s5p4d], and [16s9p5d] to O, Ti, and Ba atoms, respectively, and used in calculations of total and orbital energies of (TiO+2)-Ti-1 and (BaO)-Ba-1 fragments for quality evaluation in molecular studies. For O atom, the [6s4p] basis set is enriched with d polarization function and used along with the [10s5p4d] and [16s9p5d] basis sets for the theoretical study of the piezoelectric effect of perovskite (BaTiO3). The results of this work evidence that the piezoelectric properties in BaTiO3 can be caused by electrostatic interactions. (C) 2003 Elsevier B.V. All rights reserved.

Using shifts in the electronic emission curve to evaluate polymer surface degradation

The polymer surface degradation and/or modification evolution of Teflon FEP and Mylar C films caused by a low energy electron beam were analyzed using a new method that consists in measuring the second crossover energy shift in the electronic emission curve. Upon prolonged irradiation, the second crossover energy shifts irreversibly to lower values in Teflon FEP but to higher values in Mylar C, indicating distinct mechanisms of surface degradation for the two polymers. The method represents a relatively inexpensive way to monitor early stages of surface degradation since the secondary electron emission comes from a maximum depth below the geometric surface of 100 mn in insulators. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Gaussian basis sets by generator coordinate Hartree-Fock method to ab initio calculations of electron affinities of enolates

The Generator Coordinate Hartree-Fock (GCHF) method is employed to generate uncontracted 15s and 18s11p gaussian basis sets for the H, C and O atoms, respectively. These basis sets are then contracted to 3s and 4s H atom and 6s5p, for C and O atoms by a standard procedure. For quality evaluation of contracted basis sets in molecular calculations, we have accomplished calculations of total and orbital energies in the Hartree-Fock-Roothaaii (HFR) approach for CH, C(2) and CO molecules. The results obtained with the uncontracted basis sets are compared with values obtained with the standard D95, 6-311G basis sets and with values reported in the literature. The 4s and 6s5p basis sets are enriched with polarization and diffuse functions for atoms of the parent neutral systems and of the enolates anions (cycloheptanone enolate, 2,5-dimethyleyelopentanone enolate, 4-heptanone enolate, and di-isopropyl ketone enolate) from the literature, in order to assess their performance in ab initio molecular calculations, and applied for calculations of electron affinities of the enolates. The calculations were performed at the DFT (BLYP and B3LYP) and HF levels and compared with the corresponding experimental values and with those obtained by using other 6-3 1 + +G((*)) and 6-311 + +G((*)) basis sets from literature. For the enolates studied, the differences between the electron affinities obtained with GCHF basis sets, at the B3LYP level, and the experimental values are -0.001, -0,014, -0.001, and -0.001 eV. (C) 2002 Elsevier B.V. B.V. All rights reserved.