Experimental and theoretical cross section data of deuteron induced nuclear reactions on platinum

Journal of Radioanalytical and Nuclear Chemistry - Additional experimental activation cross sections for deuteron induced reactions on platinum were measured in the 35–49 MeV energy...     

Electronic properties of oxides: Chemical and theoretical approaches

An original analysis of the electronic and chemical properties of oxides is proposed based on the electronegativity χ and the chemical hardness η. This model which has been applied to various oxide based metals, degenerate semiconductors and optical properties of transition metal oxides allows explaining their electronic behaviors: Strong electronegativity and weak chemical hardness characterize oxides of transition elements with high oxidation state. Strong electronegativity and strong chemical hardness feature insulators with a large optical gap. Weak electronegativity and moderate chemical hardness describe alkali and alkaline earth oxides and weak electronegativity and strong chemical hardness are for ionic oxides with a relatively large optical gap. For a few illustrative case studies, ab intio electronic band structure calculations within the density functional theory framework are used.     

Determination of relative and absolute abundance of stable nitrogen isotopes by proton induced nuclear reactions

Thick-target yield of γ-rays emitted in the reactions¹⁴N(p,p′γ₁)¹⁴N and¹⁵N(p,αγ₁)¹²C were measured as a function of bombarding energy in order to select the conditions favoring the employment of these reactions in nitrogen isotopic analysis. The applicability of these reactions in the determination of relative as well as absolute nitrogen isotopic abundances was demonstrated at 4.3 MeV bombarding energy. Supported in part by the International Atomic Energy Agency, Vienna, Austria.     

Experimental and theoretical results on palladium-catalyzed hydrogenation reactions

A correlation between the stereoselectivity of cis-and trans-1, 2-dimethylcyclohexane in o-xylene hydrogenation and theoretical charge density of Pd centers as a function of particle size has been established.

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— -1, 2- o- Pd .

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On sabbatical leave from Instituto de Fisica UNAM.     

Visible light induced intermolecular [2+2]-cycloaddition reactions of 3-ylideneoxindoles through energy transfer pathway

A highly diastereoselective and regioselective [2+2]-cycloaddition reaction of 3-ylideneoxindoles has been accomplished using visible light photocatalysis. This visible light photocatalytic protocol allows an expedient access to diversely functionalized and structurally constrained oxindole derivatives containing two spirocycles and four stereogenic centers, including two all-carbon quaternary centers.     

Shear influences on polymer blends: experimental,theoretical approaches and technical implications

We examine the effects of shear on polymer blends consisting of partially miscible components, i.e. systems close to the phase boundary. The eminent phenomenon is the shift of the phase boundary, either extending the homogeneous area (flow‐induced mixing) or the opposite effect (flow‐induced demixing). The kinetics of the demixing process and concentration fluctuations are also influenced by flow fields, inducing anisotropy due to the flow direction. Experiments (scattering, rheology, in‐situ flow‐scattering, microscopy, DSC) are carried out with the academic model blend polystyrene/poly(vinyl methyl ether) and the industrial poly(styrene‐co‐maleic anhydride)/poly (methyl methacrylate) blend. The experimental results are rationalised in terms of a generalised Gibbs energy of mixing by including the energy which is stored in the sheared fluids.     

Kinetic parameters for gas-phase reactions: experimental and theoretical challenges

This article aims to illustrate the added value provided to experimental kinetics investigations by complementary theoretical kinetics studies, using as examples (i) reactions of two major hydrocarbon flame radicals, HCCO and C(2)H, and (ii) reactions of several oxygenated organic compounds with hydroxyl radicals of interest to atmospheric chemistry. The first part, on HCCO and C(2)H kinetics, does not attempt to give an extensive literature review, but rather addresses some major experimental techniques, mainly specific ones, that have allowed a great part of the available reactivity databases on these two species to be established. For several key reactions, it is shown how potential energy surfaces and statistical rate predictions based thereon have provided insight into the molecular mechanisms and have allowed estimates of product distributions as well as reliable extrapolations of experimental rate coefficients and branching ratios to higher temperatures. The second part addresses current issues in atmospheric chemistry relating mainly to hydroxyl radical reactions with oxygenated organics, and focuses on the experimental characterization of the often unusual temperature dependence of their rate coefficients and on the theoretical rationalization thereof, through the formation of hydrogen-bonded pre-reactive complexes and resulting tunnelling-enhanced H-abstraction. Finally, the development of general structure-activity relationships for OH reactions with organics, H-abstractions as well as OH-additions for unsaturated compounds, is briefly discussed.     

Assessing the nucleophilic character of 2-amino-4-arylthiazoles through coupling with 4,6-dinitrobenzofuroxan: Experimental and theoretical approaches based on structure-reactivity relationships

A kinetic study of the reactions of potentially bioactive 2-amino-4-arylthiazoles with highly reactive 4,6-dinitrobenzofuroxan (DNBF) is reported herein in acetonitrile solution. The complexation reaction was followed by recording the UV–vis spectra with time at λ_max = 482 nm. Electronic effects of substituents influencing the rate of reaction have been studied using structure-reactivity relationships. It is shown that the Hammett plot relative to the reaction of DNBF with 2-amino-4-(4-chlorophenyl)thiazole exhibit positive deviation from the log k₁ versus σ correlation, while it showed excellent linear correlation in terms of Yukawa–Tsuno equation. It has be noticed that the nonlinear Hammett plot observed for 2-amino-4-(4-chlorophenyl) thiazole is not attributed to a change in rate-determining step but is due to nature of electronic effect of substituent caused by the resonance of stabilization of substrates. The second-order rate constant (k₁) relating to the bond C–C and C-N forming step of the complexation processes of DNBF with 4-substituted-aminothiazoles and 2-amino-5-methyl-4-phenylthiazole, respectively, is fit into the linear relationship log k = s_N (N + E), thereby permitting the assessment of the nucleophilicity parameter (N) of the 2-amino-4-arylthiazoles of the range (4.90 < N < 6.85). 2-amino-4-arylthiazoles is subsequently ranked by positioning its reactivity on the general nucleophilicity scale developed recently by Mayr and coworkers (2003) leading an interesting and a direct comparison over a large domain of π-, σ -, and n-nucleophiles. The global electrophilicity/nucleophilicity reactivity indexes of the 2-amino-4-arylthiazoles have been investigated by means of a density functional theory (DFT) method. .     

ChemInform Abstract: Tl10Hg3Cl16: Single Crystal Growth,Electronic Structure and Piezoelectric Properties.

High‐quality single crystals of Tl₁₀Hg₃Cl₁₆ are grown by the Bridgman—Stockbarger method employing TlCl and HgCl₂ in the molar ratio of 7:3 (evacuated conical bottom quartz container, 1.     

On the mechanisms of the reactions between some perfluorinated compounds and CH(5) (+) --experimental and theoretical approaches

Five perfluorocompounds [perfluoropentane, 4-(perfluoroethoxy)-perfluorobutane, 5-(perfluoroethyl)-perfluorotetrahydrofuran, 2-(trifluoromethyl)-perfluorotetrahydropyran, and 4-(trifluoromethyl)-perfluorotetrahydropyran] were analyzed by electron ionization (EI) and chemical ionization (CI), using methane and isobutane as reagent gases. Under CI conditions, isobutane does not lead to significative results whereas methane leads to high ionic yields [with respect to both CI (isobutane) and EI]. Under EI conditions, practically only fragment ions are observed, with the complete loss of molecular weight. In contrast under CI(CH(4) ) conditions, [M-F](+) ions are produced. Under these conditions, the behavior of oxygen-containing molecules is strongly different from that of perfluoropentane. This is because oxygen can greatly stabilize the formation of the [M-F](+) carbocation by a π-electron donor effect, especially in the case of cyclic structures. Moreover, π-stabilization can be considered a useful tool to rationalize the position of tertiary carbon atom in trifluoromethyl-perfluoro-pyrane isomeric ions. The experimental data formed the starting point for the theoretical calculation, which allowed us to explore the mechanisms of the reactions of CH(5) (+) ions with selected perfluorocompounds. The computational methods used show that a direct protonation of the perfluoroethers (PFEs) by CH(5) (+) as well as iBu(+) is very unlikely. In the theoretical calculations, the PFE molecule served rather as the F(-) donor, and the elimination of HF molecule occurred when the PFE molecule was placed close to H(+) or CH(5) (+) ions. The fact that the latter is very unstable and decomposes to a proton and methane molecule explains why the use of methane in CI is so successful in the generation of [M-F](+) ion. In contrast, the isobutonium cation rearranges to an isopropyl cation/methane complex rather than that it abstracts F(-) from the PFE molecule. Similar results can be expected for other PFEs and perfluoroalkanes (PFAs) because both CH(5) (+) and H(+) were able to abstract the HF molecule also by attacking along the perfluoroalkyl chain of the PFE.     

Enriched stable isotopes for 123I production: Pathways and prospects

Large-scale production of radioisotopes for medical application was impeded by limited capabilities of the electromagnetic separation. Nowadays the centrifuge separation process involves more than two dozens of chemical elements. The cost of isotopes is incomparably lower than of those produced by electromagnetic separation, which has made enriched isotopes more practicable and has extended their application scope. The development of new isotope targets has ensured the realization of more effective schemes of ¹²³I production. The processes of ¹²⁴Xe and ¹²³Te production are reviewed.     

Chlorination reaction behavior of Zircaloy-4 hulls: experimental and theoretical approaches

Chlorination reaction behavior of Zircaloy-4 (Zry-4) cladding hulls was demonstrated by using a quartz reactor system. By reacting at 380 °C for 3 h, mass of the Zry-4 hulls decreased by 65.8 wt% with Cl₂ utilization of 87.1 mol%. Composition of collected product was analyzed and it was revealed that concentration of Zr was higher than 99.97 wt%. The purity of Zr in the experimental result was higher than expectation when considering Sn (1.31 wt%) and Fe (0.25 wt%) contents which can produce gaseous SnCl₄ and FeCl₃ at the experimental condition. Theoretical calculations were performed to clarify the high purity of Zr by using the HSC code. The simulation results revealed that formation of ZrCl₄ is more preferred than SnCl₄, FeCl₃, and CrCl₃. The preference of chloride formation was confirmed by the theoretical calculation, and it was suggested that the major constituents of Zry-4 might react with Cl₂ to produce chlorides in an order of ZrCl₄ > CrCl₃ > SnCl₄ > FeCl₃. It was also suggested that continuous removal of ZrCl₄ and sufficient supply of Zr source during the chlorination reaction might have contributed to the high purity of Zr.     

Vinylogous Mannich reactions: some theoretical studies on the origins of diastereoselectivity

[reaction: see text] Ab initio calculations at the RHF/3-21G level were used to investigate the limiting transition states in the addition of 2-methoxyfuran to a pyrrolinium ion. Four stationary points were found on the potential energy surface with relative energies of threo Diels-Alder, 0.0 kcal/mol; erythro open, 0.9 kcal/mol; erythro Diels-Alder, 1.3 kcal/mol; and threo open, 1.8 kcal/mol.     

Hydrogenation reactions of ethylene on neutral vanadium sulfide clusters: experimental and theoretical studies

The reactions of C(2)H(4) with H(2) on neutral vanadium sulfide clusters in a fast flow reactor are investigated by time-of-flight mass spectrometry employing 118 nm (10.5 eV) single photon ionization. The experimental products of these reactions are V(m)S(n)C(2)H(x) (m=1, n=1-3; m=2, n=1-5, and x=4-6). Observation of these products indicates that these V(m)S(n) clusters have high catalytic activity for hydrogenation reactions of C(2)H(4). Density functional theory calculations at the BPW91/TZVP level are carried out to explore the geometric and electronic structures of the V(m)S(n) clusters and to determine reaction intermediates and transition states, as well as reaction mechanisms. All reactions are estimated as overall barrierless or with only a small barrier (0.1 eV), and are thermodynamically favorable processes at room temperature. The ethylene molecule is predicted to connect with active V atoms through its π-orbital or form a σ-bond with active V atoms of catalytic V(m)S(n) clusters. The S atoms bonding with active V atoms play an important role in the dissociation of the H(2) molecule; H atoms transfer to the C(2)H(4) (one after another) following breaking of the H-H bond. A catalytic cycle for C(2)H(4) hydrogenation reactions on a vanadium sulfide catalyst surface is suggested based on our experimental and theoretical investigations.     

Alpha and deuteron induced reactions on vanadium

The stacked foil technique was used in combination with γ-ray spectroscopy to obtain excitation functions for the production of different nuclei using natural vanadium as target and 85 MeV α-particles and 46.5 MeV deuterons as projectiles. The data are compared with theoretical predictions provided by an equilibrium and pre-equilibrium reaction model. In most cases the theoretical predictions seriously under-estimated the measured cross sections.     

Evaluation of proton induced reactions on 100Mo: New cross sections for production of 99 mTc and 99Mo

The use of the ⁹⁹Mo^99mTc generator in nuclear medicine is well established world wide. The production of the ⁹⁹Mo (T_1/2 = 66 h) parent as a fission product of ²³⁵U is largely based on the use of reactor technology. From the early 1990's accelerator based production methods to provide either direct produced ^99mTc or the parent ⁹⁹Mo, were studied and suggested as potential alternatives to the reactor based production of ⁹⁹Mo. A possible pathway for the charged particle production of ^99mTc and ⁹⁹Mo is irradiation of molybdenum metal with protons via the reaction ¹⁰⁰Mo(p,2n)^99mTc and ¹⁰⁰Mo(p,pn)⁹⁹Mo, respectively. The earlier published excitation functions show large differences in their maximum that result in large differences in the calculated yields. We therefore decided to study the excitation function for these proton-induced reactions. In this work the newly measured excitation functions as well as an evaluation of earlier measured data and a discussion of the observed disagreements are presented.     

A theoretical model of solid state phase reactions: Hysteresis and kinetics

Hysteresis in the pressure-dependent solid state phase transition Pr₇O₁₂Pr₉O₁₆ is modeled using a thermodynamic formalism. The system is considered to be formed of a fixed number of domains, which are differentiated on the basis of size. The two cases of noninteracting and interacting domains are considered. The interacting domains model allows a better fit to experimental results. In each case, the model is applied to four different isothermal hysteresis curves for the Pr₇O₁₂Pr₉O₁₆ phase transition. The kinetics of the phase transition are studied for the case of noninteracting domains.     

A structural and spectroscopic study on para-aminohippuric acid with experimental and theoretical approaches

In this work, the molecular conformation, vibrational and electronic analysis of para-aminohippuric acid (pAHA, C(9)H(10)N(2)O(3)) were presented for the ground state using experimental techniques (FT-IR, FT-Raman and UV) and density functional theory (DFT) employing B3LYP exchange correlation with the 6-311++G(d,p) basis set. FT-IR and FT-Raman spectra were recorded in the regions of 400-4000cm(-1) and 50-4000cm(-1), respectively. The UV absorption spectra of the compound that dissolved in ethanol and water solution were recorded in the range of 190-400nm. Potential energy curve was computed by means of scanning NCCO torsion angle. The geometry optimization and the energies associated possible four conformers (C1-C4) were computed. The computational results diagnose the most stable conformer of pAHA as the C1 form. Optimized structure of compound was interpreted and compared with the earlier reported experimental values. The complete assignments of fundamental vibrations were performed on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. A study on the electronic properties, such as frontier molecular energies, absorption wavelengths and oscillator strengths, were predicted by time-dependent DFT (TD-DFT) approach, while taking solvent effects into account. To investigate non-linear optical properties: polarizability, anisotropy of polarizability and molecular first hyperpolarizability of molecule were computed. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures were calculated.