Positronium scattering by atoms and molecules at low energies

The recent theoretical and experimental activities in positronium (Ps) scattering by atoms and molecules are reviewed with special emphasis at low energies. We critically compare the results of different groups - theoretical and experimental. The theoretical approaches considered include the R-matrix and close-coupling methods applied to Ps-H, Ps-He and Ps-Li scattering, and a coupled-channel approach with a nonlocal model potential for Ps scattering by H, He, H-2, Ne, Ar, Li, Na, K, Rb, Cs and Ps and for pickoff quenching in Ps-He scattering. Results for scattering lengths, partial. total and differential cross-sections as well as resonance and binding energies in different systems are discussed. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Collision of positronium with atoms, molecules and ions using a modified coupled-channel framework

Scattering of positronium (Ps) from atoms (H, He, Ne, Ar), molecule (H(2)) and ion (He(+)) have been investigated using a coupled-channel (CC) formalism with a regularised non-local exchange potential. The advantage of using such a regularized exchange potential in the close-coupling formalism and the normalizability aspect of the solution at low energies with a minimum effective coupling are discussed. Results for the elastic and total scattering cross-sections, resonance and binding energies in Ps-H, and pick-off annihilation results in Ps-He are found to be in excellent agreement with measurements and variational predictions. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Prediction of a weakly bound excited state in the He-4(2)-Li-7 molecule

A scale-independent approach, valid for weakly bound three-body systems, is used to analyze the existence of excited Thomas-Efimov states in molecular systems with three atoms: a helium dimer together with isotopes of lithium (Li-6 and Li-7) and sodium (Na-23). With the present study and the available data, we can clearly predict that the He-4(2)-Li-7 system supports an excited state with binding energy close to 2.31 mK. (C) 2000 American Institute of Physics. [S0021-9606(00)30442-1].

Reatividade do [Fe(CO)2(eta2-CS2)(PPh 3)2] frente a compostos de Cu(I): síntese de espécies binucleares heterometálicas contendo CS2 em ponte entre Fe(0) e Cu(I)

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

Thermal decomposition and stability in a series of heterobimetallic carbonyl compounds of the type [Fe(CO)4(HgX)2] (X=Cl, Br, I)

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

1,3-dipolar cycloaddition of CS2 to the coordinated azide in the cyclopalladated [Pd(bzan)(mu-N-3)](2). Crystal and molecular structure of di(mu-N,S-1,2,3,4-thiatriazole-5-thiolate)bis[(benzylideneaniline-C-2,N)palladium(II)]

The compound [Pd(bzan)(mu -N-3)](2) 1, bzan = benzylideneaniline, was prepared from [Pd(bzan) (mu -OOCCH3)](2) by an anion exchange reaction. The 1,3-dipolar cycloaddition of carbon disulfide to the bridged coordinated azide in the cyclometallated compound I was investigated. The species resulting from this reaction, di(mu -N,S-1,2,3,4-thiatriazol-5-thiolate)bis[(benzylideneaniline)palladium(II)] 2, was characterized by IR spectroscopy and X-ray diffraction. The compound 2 is a dimer containing two [Pd(benzylideneaniline)] moieties connected by two vicinal bridging N,S-1,2,3,4-thiatriazole-5-thiolate anions in a square-planar coordination geometry for the palladium atoms.

TiO2 films organofunctionalized with 2-aminothiazole ligand and adsorbed Pd(II) ions applied in the photocatalytic degradation of phenol in an aqueous medium

This paper describes the preparation of thin titanium films via sol-gel route and their subsequent chemical modification by anchoring with 2-aminothiazole ligand and Pd(II) ion sorption, aiming to maximize the photocatalytic activity. The material was characterized by diffuse reflectance infrared Fourier transform spectroscopy, ultraviolet and visible spectrometry, X-ray diffractometry, and scanning electronic microscopy. The amount of palladium adsorbed on the film's surface, determined by graphite furnace atomic absorption spectrometry, showed a value of 2.69 x 10(16) atoms CM-2. The photocatalytic tests indicated that the functionalization with 2-aminothiazole and the adsorption of palladium (II) were determinants in the semiconductor's enhanced photocatalytic activity. (c) 2007 Elsevier B.V. All rights reserved.

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.

Cycloaddition reaction of the azido-bridged cyclometallated complex [Pd(dmba)N-3](2) with CS2. Crystal and molecular structure of DI(mu, N,S-1,2,3,4-thiatriazole-5-thiolate) bis[(N,N-dimethylbenzyl-amine-C-2,N)palladium(II)]

The 1,3-dipolar cycloaddition of carbon disulfide to the coordinated azide in the cyclometallated compound [Pd(dmba)(N-3)](2) (1), dmba = N,N-dimethylbenzylamine, was investigated. The compound obtained di(mu, N,S-1,2,3,4-thiatriazole-5-thiolate)-bis[(N,N-dimethylbenzylamine-C-2,N)palladium(II)] (2), was characterized by IR spectroscopy and X-ray diffraction. Complex (2) is dimeric with the two [Pd(N,N-dimethylbenzylamine)] moieties being connected by the two vicinal bridging N,S-1,2,3,4-thiatriazole-5-thiolate anions in a square-planar coordination for the palladium atoms.

Structure of human uropepsin at 2.45 angstrom resolution

The molecular structure of human uropepsin, an aspartic proteinase from the urine produced in the form of pepsinogen A in the gastric mucosa, has been determined by molecular replacement using human pepsin as the search model. Crystals belong to space group P2(1)2(1)2(1), with unit-cell parameters a = 50.99, b = 75.56, c = 89.90 Angstrom. Crystallographic refinement led to an R factor of 0.161 at 2.45 Angstrom resolution. The positions of 2437 non-H protein atoms in 326 residues have been determined and the model contains 143 water molecules. The structure is bilobal, consisting of two predominantly beta -sheet lobes which, as observed in other aspartic proteinases, are related by a pseudo-twofold axis. A model of the uropepsin-pepstatin complex has been constructed based on the high-resolution crystal structure of pepsin complexed with pepstatin.

Trichloro-bridged diruthenium (III,III) complexes: X-ray isomorphous structures of [Ph3X=O center dot center dot center dot H center dot center dot center dot O=XPh3][Ru2Cl7(XPh3)(2)]center dot 0.5(CH2Cl2)(H2O)(X = As or P)

The triply chloro-bridged binuclear complexes [Ph3X=O...H...O=XPh3][Ru2Cl7(XPh3)(2)].0.5(CH2Cl2) (H2O) (X = As or P) were obtained from [RuCl3(XPh3)(2)DMA].DMA (DMA = dimethylacetamide) CH2Cl2/Et2O solution. The structures were characterized by X-ray diffraction studies. The complexes are formed from two Ru atoms bridged by three chloride anions. The two ruthenium atoms are also coordinated to two non-bridging Cl atoms and an AsPh3 or PPh3 ligand respectively. As an interesting feature, the cations of these complexes are protons, trapped in a very short hydrogen bond between two triphenylarsine or triphenylphosphine oxide molecules.

Response of L-alanine and 2-methylalanine minidosimeters for K-Band (24 GHz) EPR dosimetry

Minidosimeters of L-alanine and 2-methylalanine (2MA) were prepared and tested as potential candidates for small radiation field dosimetry. To quantify the free radicals created by radiation a K-Band (24 GHz) EPR spectrometer was used. X-rays provided by a 6 MV clinical linear accelerator were used to irradiate the minidosimeters in the dose range of 0.5-30 Gy. The dose-response curves for both radiation sensitive materials displayed a good linear behavior in the dose range indicated with 2MA being more radiation sensitive than L-alanine. Moreover, 2MA showed a smaller LLD (lower limit detection) value. The proposed system minidosimeter/K-Band spectrometer was able to detect 10 Gy EPR spectra with good signal-to-noise ratio (S/N). The overall uncertainty indicates that this system shows a good performance for the detection of dose values of 20 Gy and above, which are dose values typically used in radiosurgery treatments. (c) 2007 Elsevier B.V. All rights reserved.

Local order around of germanium atoms in Ga10Ge25S65 glass by EXAFS

Irreversible photoexpansion effect has been observed in amorphous Ga10Ge2S65 glasses when its surface was exposed to light with energy greater than the band gap, 3.52 eV. A volume change of about 5% was reached in bulk samples by controlling illumination time and the laser power density. To understand the atomic scale processes of the photoexpansion effect, extended X-ray absorption fine structure (EXAFS) spectroscopy has been used as a local probe of the germanium environment in the glass samples before and after illumination. Modifications are observed in the average coordination shell around Ge atoms in the illuminated sample compared to the non-illuminated one. For the non-illuminated sample, the Ge coordination shell is described by a distorted tetrahedron of sulfur atoms at around 2.20 Angstrom. After illumination, the EXAFS signal can be explained by introducing an additional contribution to this average environment. Based on an analysis of the EXAFS data we proposed a two-shell model of 0.5 oxygen atoms at 2.01 Angstrom and 3.6 sulfur atoms at a 2.20 Angstrom. The existence of Ge-O bonds in the glass after illumination was confirmed by infrared measurements. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Mixed pseudohalide complexes of copper(II). Crystal and molecular structure of [Cu(N-3)(NCS)(tmen)](n) and of [Cu(N-3)(NCO)(tmen)]2 (tmen = N,N,N ',N '-tetramethylethylenediamine)

The compounds [Cu(N-3)(NSC)(tmen)](n) (1), [Cu(N-3)(NCO)(tmen)](n) (2) and [Cu(N-3)(NCO)(tmen)](2) (3) (tmen = N,N,N',N'-tetramethylethylenediamine) were synthesized and studied by i.r. spectroscopy. Single crystals of compounds (1) and (3) were obtained and characterized by X-ray diffraction. The structure of compound (1) consists of neutral chains of copper(II) ions bridged by a single azido ligand showing the asymmetric end-to-end coordination fashion. Each copper ion is also surrounded by the other three nitrogen atoms: two from one N,N,N',N'-tetramethylethylenediamine and one from a terminal bonded thiocyanate group. Compound (2) decomposes slowly in acetone and the product formed [Cu(N-3)(NCO)(tmen)](2) (3) crystallizes in the monoclinic system (P2(1)). The structure of (3) consists of dimeric units in which the Cu atoms are penta-coordinated and connected by p(1,3) bridging azido and cyanate ligands. In both cases the five coordinated atoms give rise to a slightly distorted square-based pyramid coordination geometry at each copper ion. The thermal behavior of [Cu(N-3)(NSC)(tmen)](n) (1) and [Cu(N-3)(NCO)(tmen)](n) (2) were investigated and the final decomposition products were identified by X-ray powder diagrams.

Local order around tungsten atoms in tungstate fluorophosphate glasses by X-ray absorption spectroscopy

X-ray absorption spectroscopy was used to study the local environment of tungsten atoms in NaPO3-BaF2,-WO3 glasses and the results were compared with crystalline references Na2WO4 and WO3. XANES measurements at the W-L-1 edge allowed to determine a distorted octahedral environment of tungsten atoms in these glasses similar to the local order of tungsten in monoclinic WO3. Extended X-ray absorption fine structure (EXAFS) has been used as a local probe to monitor the effect of WO3 concentration on the tungsten environment. Based on an analysis of the EXAFS data, we proposed a three-shell model of oxygen atoms around tungsten as in monoclinic WO3. With increasing WO3 concentration, it was found that R-2 decreases from 1.96 to 1.92 angstrom whereas R-3 increases from 2.07 to 2.12 angstrom. (c) 2005 Elsevier B.V. All rights reserved.