The interaction between atoms of Au and Cu with clean Si(111) surface: A study combining synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

GCHF basis sets and their application in the electronic structure study of PrMnO3

The approach called generator coordinate Hartree-Fock (GCHF) method is used in the selection of Gaussian basis set [25s18p for O ((3)p), 31s21p14d for Mn (S-6), and 33s22p16d9f for Pr ((4)J)] for atoms. The role of the weight functions in the assessment of the numerical integration range of the GCHF equations is shown. These basis sets are contracted to (25s18p/9s5p), (31s21p14d/9s6p4d), and (33s22pl6d9f118sl2p5d3f) by segmented contraction scheme of Dunning and they are utilized in calculations of Restricted-Open-HF (ROHF) Total and Orbital energies of the (MnO+1)-Mn-3 and (PrO+1)-Pr-1 fragments, to evaluate their quality in molecular studies. The addition of one d polarization function in the contracted (9s5p) basis set for O(P-3) atom and their application with the contracted (9s6p4d), (18s21p5d3f) basis sets for Mn (S-6) and Pr-Pr ((4)j) atoms lead to the electronic structure study of PrMnO3. The dipole moment, the total energy, and total atomic charges properties were calculated and were carried out at ROHF level with the [PrMnO3](2) fragment. The calculated values show that PrMnO3 does not present piezoelectric properties. (C) 2004 Elsevier B.V. All rights reserved.

Investigation of (CH3OH)-C-13 methanol: new laser lines and assignments

We have reinvestigated (CH3OH)-C-13 as a source of far-infrared (FIR) laser emission using a CO2 laser as a pumping source. Thirty new FIR laser lines in the range 36.5 mum to 202.6 mum were observed and characterized. Five of them have wavelengths between 36.5 and 75 mum and have sufficient intensity to be used in LMR spectroscopy. Using Fourier-transform spectroscopic data in the infrared (IR) and FIR regions we have determined the assignment for 10 FIR laser transitions and predict nine frequencies for laser lines which have yet to be observed.

Strong and fast phase modulation for quantitative analysis of photorefractive gratings

A new approach for studying photorefractive gratings in two-wave mixing experiments by a phase modulation technique is presented. The introduction of a large-amplitude, high-frequency sinusoidal phase modulation in one of the input beams blurs the interference pattern and provides powerful harmonic signals for accurate measurements of the grating diffraction efficiency eta and the output phase shift rho between the transmitted and diffracted waves. The blurring of the light fringes can be used to suppress the higher spatial harmonics of the grating, allowing a space-charge field with sinusoidal profile to be recorded. Although the presence of such a strong phase modulation affects the beam coupling in a rather complicated way, it is shown that for the special case of equal intensity input beams, the effect of the phase modulation on eta and rho is reduced to a weakening of the coupling strength. The potentialities of the technique are illustrated in a study of refractive-index waves excited by running interference patterns in a Bi12TiO20 crystal. Expressions for the diffraction efficiency and the output phase shift are derived and used to match numerically calculated curves to the experimental data. The theoretical model is supported by the very good data fitting and allows the computation of important material parameters.

CH3OH optically pumped by a (CO2)-C-13 laser: new laser lines and assignments

We report 12 new THz (far-infrared) laser lines from methanol (CH3OH), ranging from 58.1 mu m (5.2 THz) to 624.6 mu m (0.5 THz). A(13) CO2 laser of wide tunability (110 MHz) has been used for optical pumping, allowing access to previously unexplored spectral regions. Optoacoustic absorption spectra were used as a guide to search for new THz laser lines, which have been characterized in wavelength, polarization, offset, relative intensity, and optimum operation pressure. For 20 laser lines previously observed, we have measured the absorption offset with respect to the (CO2)-C-13 laser line center.

Energy transfer and frequency upconversion in Yb3+-Er3+-doped PbO-GeO2 glass containing silver nanoparticles

We report the infrared-to-visible frequency upconversion in Er3+-Yb3+-codoped PbO-GeO2 glass containing silver nanoparticles (NPs). The optical excitation is made with a laser at 980 nm in resonance with the F-2(5/2)-> F-2(7/2) transition of Yb3+ ions. Intense emission bands centered at 525, 550, and 662 nm were observed corresponding to Er3+ transitions. The simultaneous influence of the Yb3+-> Er3+ energy transfer and the contribution of the intensified local field effect due to the silver NPs give origin to the enhancement of the whole frequency upconversion spectra.

Near-infrared nonlinearity of a multicomponent tellurium oxide glass at 800 and 1,064 nm

We report on the nonlinear (NL) optical properties of glassy TeO2-GeO2-K2O-Bi2O3 at lambda = 800 nm and lambda = 1,064 nm. Using the Kerr gate technique with a laser delivering 150 fs pulses at 800 nm, we demonstrated the fast NL response of the samples. The modulus of the NL refractive index, n (2), at 800 nm was similar to 10(-15) cm(2)/W. The Z-scan technique was used to determine n (2) a parts per thousand +10(-15) cm(2)/W, at 1,064 nm with pulses of 17 ps. The two-photon absorption coefficient, alpha (2), was smaller than the minimum that we can measure (< 0.003 cm/GW). The figure of merit n (2)/alpha (2) lambda was calculated and indicates that this glass composition has large potential to be used for all-optical switching.

Writing saturated holograms in LiNbO3 crystals through phase control and double diffraction

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

Photoelastic stress analysis of splinted and unitary implant-supported prostheses

The aim of this study was to evaluate the effects that splinting and different lengths of implants have on the stress distribution in implant-supported prostheses by photoelastic analysis. A total of five photoelastic resin models were made with different proposed situations, and 400 load applications were performed for the analysis. Compared with the unitary prosthesis, the splinted implant-supported prosthesis acted favorably in the distribution of stresses and strains to the implant (p < 0.001). The increase in length was a significant factor in the stress distribution (p < 0.05) and, ultimately, the overall reduction in stress. It was concluded that the splinted implant-supported prosthesis behaved better biomechanically compared with the unitary prosthesis.

Picosecond nonlinearity of GeO2-Bi2O3-PbO-TiO2 glasses at 532 and 1,064 nm

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Laser frequency measurements and spectroscopic assignments of optically pumped 13CH3OH

A three-laser heterodyne system was used to measure the frequencies of twelve optically pumped laser emissions from 13CH3OH in the far-infrared (FIR) region. These emissions, ranging from 54 to 142 μm, are reported with fractional uncertainties up to ±2 × 10-7 along with their polarization relative to the CO2 pump. Using the 9P32 and 10R14 CO2 lines, complete spectroscopic assignments for two laser systems were confirmed.

Synthesis, spectroscopic characterization and X-ray crystallographic studies of trans-[PtCl2(PEt3)(PySOR)] complexes, where PySOR=(2-methylsulphinyl)-pyridine and (2-n-propylsulphinyl)pyridine

Alkylsulphinylpyridine ligands containing three potential donor centres: N, S and O atoms and two complexes of general formula trans-[PtCl2(PEt3)PySOR)] (R = Me and Pr-n) were prepared and characterized by elemental analysis, i.r. spectroscopy, H-1- and P-31-n.m.r. and X-ray crystallography. The ambidentate ligands act in both situations as monodentate ligands, bonded to the metal exclusively through the nitrogen atom. The crystal structures revealed the occurrence of discrete molecules and, in both complexes, the Pt atoms are coordinated in square planar arrangements by two chloride ions, in a trans configuration, by the pyridine nitrogen atom, and by the phosphine P atom. The oxygen atoms do not take part in the complexation scheme.

Light-induced relief gratings and a mechanism of metastable light-induced expansion in chalcogenide glasses

We report on a metastable light-induced volume expansion in Ge25+xGa10-xS65 glasses under irradiation with band gap (UV) light, which can result in recording of relief gratings on their surface in the case of irradiation with two interfering beams. We propose a mechanism for the expansion, which is based on the light-induced change in the polarizability of secondary (van der Waals type) bonds and the effect of this change on primary (covalent type) bonds of the glass. The effect is suggested to be due to an interference of electrons, which belong to a chalcogen atom and participate in the formation of secondary and primary bonds, respectively. We suggest that a minimum point of the Lennard-Jones potential, which corresponds to the equilibrium position of a chalcogen atom is shifted in the course of irradiation to a larger interatomic distance. This shift causes a volume expansion and allows a diffusion of chalcogen atoms into the irradiated area. We show that light-induced polymerization of the glass network is an important attribute of the light-induced volume expansion.

Synthesis, crystal structure and theoretical studies of aryltellurenyl tetramethylthiourea(tmtu) iodine complexes: Ph-Te(tmtu)I (1) and beta-naphtyl-Te(tmtu)I (2)

(1) C11H17IN2STe, Mr = 463.83, P2(1)/n, a 7.6582(8), b = 13.8008(9), c = 15.026(3) angstrom, beta = 96.233(12)degrees, Z = 4, R-1 = 0.0318. (2) C15H19IN2STe, Mr = 513.88, P2(1)/n, a = 8.434(5), b = 11.697(5), c = 18.472(5) angstrom, beta = 98.556(5)degrees, Z = 4, R-1 = 0.0236. The synthesis of the aryltellurenyl N,N',-tetramethylthiourea (tmtu) iodide has been performed by ligand exchange with potassium iodide and the corresponding aryltellurenyl(tmtu) bromide. In both structures the tellurium atom is primarily three-coordinated, being bonded to a carbon atom of the organic ring and, in directions nearly perpendicular to the Te-C bond, to one tmtu sulfur atom and one iodine. In addition there are Te...secondary bonds, joining the molecules in centrosymmetric dimers, which in turn are joined through C-H...1 and C-H... S interactions, in (1) and (2), respectively.

Methyl- and phenylmercury(II) derivatives of 2-mercaptobenzothiazole. Crystal structure of (2-mercaptobenzothiazolato)methylmercury(II)

The complexes MeHgL and PhHgL (HL = 2-mercaptobenzothiazole) have been obtained from the reaction of the ligand with methylmercury hydroxide and phenylmercury acetate, respectively, in methanol. MeHgL, which has been characterized by single-crystal X-ray diffraction analysis (crystal data: triclinic, space group P1, with a = 8.009 (4) Å, b = 10.042 (4) Å, c = 13.074 (3) Å, α = 101.25 (2)°, β = 102.61(3)°, γ = 101.42 (3)°, R = 0.067), crystallizes with two independent molecules, I and I′, contained in each asymmetric unit with a coordination geometry based on the almost linear C-Hg-S group (Hg-S = 2.369 (6) Å, Hg-C = 2.06 (2) Å, and C-Hg-S = 177.7 (7)° for I; Hg-S = 2.375 (6) Å, Hg-C = 2.10 (3) Å, and C-Hg-S = 178.8 (6)° for I′). A secondary intramolecular interaction between the mercury atom and the C=N group of the ring and some weak intermolecular interactions between the metal and sulfur atoms were also found. The vibrational spectra of this compound and the phenylmercury(II) compound are discussed in light of the crystal structure. Diagnostic criteria of the bonding modes for the ligand are assessed. © 1985 American Chemical Society.