Uranium and thorium analyses by delayed fission neutron counting technique using a small neutron generator

Applicability of a small neutron generator and a dual rectangular tube sample transfer system for analyses of U and Th using delayed fission neutron technique has been investigated. A way of optimizing the timing parameters is reported. At a fast neutron flux of 10⁸ n.cm^–2s^–1, 0.02 w% U can be determined. For thorium determination this method is less sensitive. The Cd difference technique can be used for the simultaneous determination of U and Th but it has lower sensitivity.This work was supported in part by the IAEA.     

Calcium hydride and deuteride studied by neutron diffraction and NMR

The structure of CaD₂ has been redetermined by neutron diffraction and the structure has been confirmed by NMR measurements. However, the interpretation of the NMR measurements is not easy. The unsymmetrical position of the hydrogen (deuterium) atoms and the large range of interatomic distances lead to complicated spectra. Since the spectra for both the hydride and the deuteride seem to be determined mainly by dipolar interactions, one can conclude that the electric field gradient at the D sites must be very small. Line narrowing above 440°K is ascribed to proton diffusion with an activation enthalpy of 17.4 kcal/mol.     

Investigation of structure of liquid 2,2,2 trifluoroethanol: neutron diffraction, molecular dynamics, and ab initio quantum chemical study

The molecular conformation and intermolecular H bonding in liquid 2,2,2 trifluoroethanol (TFE) have been studied by neutron diffraction with hydrogen/deuterium isotopic substitution at room temperature. For comparison, conformations of molecules and their dimers in the gas phase have also been calculated, based on the density functional theory. Energies, geometry, and vibrational frequencies of dimers were analyzed. Diffraction data analyzed by the "Monte Carlo determination of g(r)" (MCGR) method resulted in a molecular structure in agreement with the findings from gas phase electron diffraction experiments and density functional calculations. The intermolecular structure functions were compared to the same functions obtained from a molecular dynamics simulation. All of the composite radial distribution functions are in good agreement with the simulation results. According to our calculation the hydrogen-bonded aggregation size is smaller in pure liquid TFE than in pure liquid ethanol.     

Uranium and thorium determination in Brazilian coals by epithermal neutron activation analysis

An experimental technique has been developed to determine impurities in coal. Uranium was determined by counting the²³⁹Np 106.1 keV -ray with a LEPS detector and thorium by counting the²³³Pa 311.8 keV -ray with a Ge(Li) detector. Seventeen coal samples were analyzed with an average precision of 3% and a quantitative determination limit of 0.153 g/g for uranium and 0.078 g/g for thorium. The technique allows determinations of up to twenty elements besides U and Th and can be applied in routine analysis.     

Tautomeric and conformational properties of acetoacetamide: electron diffraction and quantum chemical study

The tautomeric properties of acetoacetamide, CH3C(O)CH2C(O)NH2, have been investigated by gas electron diffraction (GED) and quantum chemical calculations (B3LYP and MP2 approximations with 6-31G(d,p) and 6-311++G(3df,pd) basis sets). GED results in a mixture of 63(7)% enol tautomer and 37(7)% diketo form at 74(5) degrees C. Only one enol form with the O-H bond adjacent to the methyl group (CH3C(OH)=CHC(O)NH2) and only one diketo conformer (with dihedral angles tau(O=C(CH3)-C-C) = 31.7(7.5) degrees and tau(O=C(NH2)-C(H2)-C(O)) = 130.9(4.5) degrees ) are present. The calculated tautomeric composition varies in a wide range depending on the quantum chemical method and basis set. Only the B3LYP method with small basis sets reproduces the experimental composition correctly.     

Propene adsorption sites in zeolite ITQ-12: a combined synchrotron X-ray and neutron diffraction study

The adsorption site of propene in the small-pore, pure silica zeolite [Si24O48]-ITW-ITQ-12 has been characterized via Rietveld refinement of the crystal structure of propene-loaded ITQ-12 on the basis of synchrotron X-ray and neutron diffraction data taken at 298 K. The structure can be described with a monoclinic unit cell having Cm symmetry and unit cell parameters a = 10.436 angstroms, b = 15.018 angstroms, c = 8.855 angstroms, beta = 105.74 degrees, and volume = 1335.9 angstroms3. Four-fold disordered adsorption sites that are nearly equivalent relative to the cage's 2/m pseudosymmetry are located near the center of each ellipsoidally shaped [4(4)5(4)6(4)8(4)] cage. At this site, the adsorbed propene molecule lies on a plane close and approximately parallel to the equatorial plane of the cage and is aligned with its methylene group pointing toward the pore's eight-ring window. The refined propene concentration, 1.8 per unit cell content, is close to one propene molecule per [4(4)5(4)6(4)8(4)] cage and the amount observed in adsorption experiments at 298 K and 1 atm propene partial pressure.     

Molecular structure of magnesium dibromide: an electron diffraction and quantum chemical study

The molecular structure of magnesium dibromide was investigated by high-level computational techniques and gas-phase electron diffraction. The vapor consisted of about 88% monomeric and 12% dimeric species at the electron diffraction experimental conditions at 1065 K. The geometrical parameters and vibrational characteristics of monomeric, dimeric, and trimeric magnesium dibromide species were determined by computations. Very high level computations with extended basis sets and relativistic pseudopotentials on bromine were needed to reach an agreement between computed and estimated experimental equilibrium geometries for the monomer. For both the dimer and the trimer, different geometrical arrangements were tested. Their ground-state structures have halogen bridges with four-membered ring geometries and D2h and D2d symmetry, respectively. Thermodynamic parameters have also been calculated.     

Comparative quantum chemical study of cyclic ether-water complexes

The interaction of the cyclic ethers tetrahydrofuran (THF) and 1,4-dioxane (DO) with water molecules in 1: 1 and 1: 2 ratios and with water dimers has been investigated by the density functional theory method in the B3LYP/6–31+G** approximation. The most stable structures and geometric and energetic characteristics of the resulting complexes have been determined, and the atomic charges have been calculated. The inferences from this study have been corroborated by comparing the properties of aqueous solutions of THF and DO.     

Proton mobility in protonated glycylglycine and N-formylglycylglycinamide: a combined quantum chemical and RKKM study

Theoretical model calculations were performed to investigate the degree of validity of the mobile proton model of protonated peptides. The structures and energies of the most important minima corresponding to different structural isomers of protonated diglycine and their conformers, as well as the barriers separating them, were determined by DFT calculations. The rate coefficients of the proton transfer reactions between the isomers were calculated using the RRKM method in order to obtain a quantitative measure of the time scale of these processes. The proton transfer reactions were found to be very fast already at and above the threshold to the lowest energy decomposition pathway. Two possible mechanisms of b2+-ion formation via water loss from the dipeptide are also discussed. The rate-determining step of the proton migration along a peptide chain is also investigated using the model compound N-formylglycylglycinamide. The investigations revealed that this process very possibly occurs via the protonation of the carbonyl oxygens of the amide bonds, and its rate-determining step is an internal rotation-type transition of the protonated C=O-H group between two adjacent C=O-HellipsisO=C bridges.     

Ambidentate and redox-properties of 4,7-phenanthroline-5,6-dione in cobalt complexes: a quantum chemical study

Mono- and dinuclear adducts of cobalt diketonates with tetradentate 4,7-phenanthroline- 5,6-dione were modeled within the framework of DFT UB3LYP*/6-311++G(d,p) approximation. A competitive coordination of the metal ion to different donor centers of the redox-active ligand was studied. Variation of substituents in the diketone moieties allowed one to reveal compounds than can undergo thermally initiated one- and two-step valence tautomeric rearrangements. The calculated energy and magnetic characteristics of the dinuclear complexes give reasons to consider them as potential basis of molecular electronics and spintronics devices.     

The coordination of uranyl in water: a combined quantum chemical and molecular simulation study

The coordination environment of uranyl in water has been studied using a combined quantum mechanical and molecular dynamics approach. Multiconfigurational wave function calculations have been performed to generate pair potentials between uranyl and water. The quantum chemically determined energies have been used to fit parameters in a polarizable force field with an added charge transfer term. Molecular dynamics simulations have been performed for the uranyl ion and up to 400 water molecules. The results show a uranyl ion with five water molecules coordinated in the equatorial plane. The U-O(H(2)O) distance is 2.40 A, which is close to the experimental estimates. A second coordination shell starts at about 4.7 A from the uranium atom. No hydrogen bonding is found between the uranyl oxygens and water. Exchange of waters between the first and second solvation shell is found to occur through a path intermediate between association and interchange. This is the first fully ab initio determination of the solvation of the uranyl ion in water.     

O-O bond cleavage in dinuclear peroxo complexes of iron porphyrins: a quantum chemical study

To gain insight into the mechanisms of O2 activation and cleavage in metalloenzymes, biomimetic metal complexes have been constructed and experimentally characterized. One such model complex is the dinuclear peroxo complex of iron porphyrins observed at low temperature in a non-coordinating solvent. The present theoretical study examines the O-O bond cleavage in these complexes, experimentally observed to occur either at increased temperature or when a strongly coordinating base is added. Using hybrid density functional theory, it is shown that the O-O bond cleavage always occurs in a state where two low-spin irons (S = +/-1/2) are antiferromagnetically coupled to a diamagnetic state. This state is the ground state when the strong base is present and forms an axial ligand to the free iron positions. In contrast, without the axial ligands, the ground state of the dinuclear peroxo complex has two high-spin irons (S = +/-5/2) coupled antiferromagnetically. Thus, the activation barrier for O-O bond cleavage is higher without the base because it includes also the promotion energy from the ground state to the reacting state. It is further found that this excitation energy, going from 10 unpaired electrons in the high-spin case to 2 in the low-spin case, is unusually difficult to determine accurately from density functional theory because it is extremely sensitive to the amount of exact exchange included in the functional.     

Environment effects on the CO vibrational shifts in erbium complexes: a quantum chemical study

The stability of lanthanide complexes and the efficiency of the energy transfer process, which makes these molecules interesting materials for technological applications, are correlated to the chemical environment surrounding the metal ion. In particular the efficiency depends on the relative position of the antenna (the ligand moiety that acts as photon absorption center) and the lanthanide ion (the emitting center), while the stability of the complex is correlated to the strength of the coordination between the rare earth and the ligands. For these reasons, knowledge of the structural properties of the complex is an interesting task to achieve. Since a large number of ligand structures hold the carboxylate group (COO(-)), which is used as an anchor for binding the antennae to the lanthanide ion, in this work we will show how the vibrational shifts of this group, induced by the interactions between the carboxylate moiety and the metal center of the lanthanide complex, can be used for obtaining in a simple way information on the structure of the chemical environment surrounding the lanthanide ion.     

X-ray diffraction, magnetochemical, and quantum chemical study of the structure and properties of binuclear copper(II) complexes

The binuclear chelates of copper(II) based on the tridentate azomethine ligands were synthesized and characterized by elemental analysis, IR, ¹H NMR spectroscopy, X-ray absorption spectroscopy (XANES and EXAFS), and magnetic measurements. The quantum-chemical study of the structure and calculation of magnetic properties of the obtained metal-chelates was performed using the density functional theory with the broken symmetry technique. The performed magnetochemical studies in the temperature range 2?C300 K suggest the existence of antiferromagnetic exchange interaction in all obtained complexes. The parameters of the exchange interaction ?2J > 260 cm^?1 were determined experimentally for all compounds, the experimental data is in a good agreement with the results of quantum-chemical calculations.     

A quantum chemical study of trimethoxyaluminum complexes with neutral molecules

The spatial and electronic structures of trimethoxyaluminum complexes with neutral molecules are calculated by the MP2/6-31(2d,p) method using the PC GAMESS-Firefly program package. The main characteristics of aluminum bonds in these molecules are determined by AIM and NBO methods. It is shown that these bonds can be characterized as the bonds between the atoms with closed shells.     

Gas electron diffraction and quantum chemical study of the structure of a 2-nitrobenzenesulfonyl chloride molecule

A combined gas electron diffraction and quantum chemical (B3LYP/6-311+G**, B3LYP/cc-pVTZ, B3LYP/cc-pVTZ, midix (Cl), and MP2/cc-pVTZ) study of the structure of a 2-NO₂-C₆H₄-SO₂Cl molecule is performed. It is found experimentally that at a temperature of 345(5) K the gas phase contains two conformers of the C ₁ symmetry. Conformer I with a nearly perpendicular arrangement of the S-Cl bond with respect to the benzene ring plane (the C(NO₂)-C-S-Cl torsion angle is 84(3)°) is contained predominantly (69(12)%). In conformer II, the S-Cl bond is located near the benzene ring plane (the C(NO₂)-C-S-Cl angle is 172(3)°). The following experimental internuclear distances (Å) are obtained for conformer I: r _h1(C-H) = 1.064(15), r _h1(C-C)_av = 1.397(3), r _h1(C-S) = 1.761(6), r _h1(S-O)_av = 1.426(4), r _h1(S-Cl) = 2.043(5), r _h1(N-O)_av = 1.222(4), r _h1(C-N) = 1.485(16). In both conformers, the NO₂ group is turned by more than 30° relative to the benzene ring plane.     

Calixarenes as hosts for ammonium cations: a quantum chemical study and mass-spectrometric investigations

Host-guest complexes of tetramethylcavitand with different ammonium cations were investigated by using a quantum chemical method at the density functional level (BP86, B3 LYP). The NH4+ cation is strongly bound to the host. Increasing methyl substitution at the cation decreases its inclination towards the complex formation. The calculated data are in line with results from electrospray ionization mass spectrometry (ESI-MS) experiments. They reveal stable aggregates only for the NH4+ cation and for the primary alkylammonium cations.     

Controlling phosphorescence color and quantum yields in cationic iridium complexes: a combined experimental and theoretical study

We report a combined experimental and theoretical study on cationic Ir(III) complexes for OLED applications and describe a strategy to tune the phosphorescence wavelength and to enhance the emission quantum yields for this class of compounds. This is achieved by modulating the electronic structure and the excited states of the complexes by selective ligand functionalization. In particular, we report the synthesis, electrochemical characterization, and photophysical properties of a new cationic Ir(III) complex, [Ir(2,4-difluorophenylpyridine)2(4,4'-dimethylamino-2,2'-bipyridine)](PF(6)) (N969), and compare the results with those reported for the analogous [Ir(2-phenylpyridine)2(4,4'-dimethylamino-2,2'-bipyridine)](PF(6)) (N926) and for the prototype [Ir(2-phenylpyridine)2(4,4'-tert-butyl-2,2'-bipyridine)](PF(6)) complex, hereafter labeled N925. The three complexes allow us to explore the (C/\N) and (N/\N) ligand functionalization: considering N925 as a reference, we investigate in N926 the effect of electron-releasing substituents on the bipyridine ligand, while in N969, we investigate the combined effect of electron-releasing substituents on the bipyridine ligand and the effect of electron-withdrawing substituents on the phenylpyridine ligands. For N969 we obtain blue-green emission at 463 nm with unprecedented high quantum yield of 85% in acetonitrile solution at room temperature. To gain insight into the factors responsible for the emission color change and the different quantum yields, we perform DFT and TDDFT calculations on the ground and excited states of the three complexes, characterizing the excited-state geometries and including solvation effects on the calculation of the excited states. This computational procedure allows us to provide a detailed assignment of the excited states involved in the absorption and emission processes and to rationalize the factors determining the efficiency of radiative and nonradiative deactivation pathways in the investigated complexes. This work represents an example of electronic structure-driven tuning of the excited-state properties, thus opening the way to a combined theoretical and experimental strategy for the design of new iridium(III) phosphors with specific target characteristics.