Validity of the equivalent-photon approximation for the production of massive spin-1 particles

We point out that the equivalent-photon approximation (EPA) for processes with massive spin-1 particles in the final state would have validity in a more restricted kinematic domain than for processes where it is commonly applied, viz., those with spin-1/2 or spin-0 particles in the final state. We obtain the criterion for the validity ofEPA for the two-photon production of a pair of charged, massive, point-like spin-1 particlesV ^±, each of massM and with a standard magnetic moment (κ=1). In a process in which one of the photons is real and the other virtual with four-momentumq, the condition for the validity ofEPA is |q ²|≪M ², in addition to the usual condition |q ²|≪W ²,W being theV ⁺ V ⁻ invariant mass. In a process in which both photons are virtual (with four-momentaq andq′), our condition is |q ²||q′²|W ⁴ ≪ 16M ⁸, in addition to |q ²| ≪M ², |q′²| ≪M ² and |q ²| ≪W ², |q′²| ≪W ². Even when these extra conditions permitting the use ofEPA are not fulfilled, convenient approximate expressions may still be obtained assuming merely |q ²| ≪W ² and |q′²| ≪W ². We also discuss how the extra conditions are altered when the vector bosons are incorporated in a spontaneously broken gauge theory. Examples ofW boson production in Weinberg-Salam model are considered for which the condition |q ²||q′²|W ⁴ ≪ 16M ⁸ is shown to be removed.     

A method for computing the solubility limit of solids: application to sodium chloride in water and alcohols

We present an adaptable method to compute the solubility limit of solids by molecular simulation, which avoids the difficulty of reference state calculations. In this way, the method is highly adaptable to molecules of complex topology. Results are shown for solubility calculations of sodium chloride in water and light alcohols at atmospheric conditions. The pseudosupercritical path integration method is used to calculate the free energy of the solid and gives results that are in good agreement with previous studies that reference the Einstein crystal. For the solution phase calculations, the self-adaptive Wang-Landau transition-matrix Monte Carlo method is used within the context of an expanded isothermal-isobaric ensemble. The method shows rapid convergence properties and the uncertainty in the calculated chemical potential was 1% or less for all cases. The present study underpredicts the solubility limit of sodium chloride in water, suggesting a shortcoming of the molecular models. Importantly, the proper trend for the chemical potential in various solvents was captured, suggesting that relative solubilities can be computed by the method.     

Alternative mechanisms for cyanide anion exchange with acetonitrile

Mechanisms for the recently observed exchange of cyanide anion in acetonitrile have been investigated by means of semi-empirical MNDO molecular orbital calculations. A prototropic type mechanism $\text{via}$ a cyclopropane intermediate is the most likely candidate. The previously proposed concerted migration is indicated to be the least favourable reaction pathway.     

Physicochemical studies of green phosphorescent light-emitting materials from cyclometalated heteroleptic iridium(III) complexes

A series of novel imidazole ligands were synthesized and characterized. Phosphorescence studies of series of heteroleptic cyclometalated iridium(III) complexes reveal that these complexes possess dominantly (3)MLCT and (3)π-π* excited states and the solvent shifts of these complexes are interpreted by Richardt-Dimroth and Marcus solvent functions. The results consistent with prior assignments on the absorption band to a metal-to-ligand charge transfer excited state associated with chelating ligand. Emission kinetic studies exploited that the radiative transition (k(r)), increases with increasing λ(em) and linear correlation exists between ln(k(nr)) and energy gap. Electronic transition theory is applied to study the effect of E(g) and ΔQ(e) on non-radiative transition (k(nr)). With a larger ΔQ(e), favouring vibrational overlap and leading to a larger value for k(nr).     

Kinetics and mechanism of oxidation of N,α-diphenylnitrones by 4-(dimethylamino)pyridinium chlorochromate (DMAPCC) in aqueous DMF medium

The kinetics of oxidation of aldonitrones by 4-(dimethylamino)pyridinium chlorochromate (DMAPCC) has been studied in aqueous N,N-dimethylformamide in the presence of perchloric acid. The reaction follows first-order kinetics with respect to each of DMAPCC and nitrone. The order with respect to [H⁺] was found to be close to zero. The rate of oxidation was unaltered by the variation of [NaClO₄] but addition of MnSO₄ decreased the rate. The reaction rate was found to decrease with a decrease in dielectric constant of the medium. Electron-releasing and electron-withdrawing groups perturb the reaction rate with a good Hammett correlation. The oxidation products were found to be benzaldehyde and nitrosobenzene. The reaction was carried out at four different temperatures and the activation parameters have been calculated. On the basis of the experimental findings, a suitable mechanism has been proposed.     

Sample Treatment Approaches for Trace Level Determination of Cesium in Hepatitis B Vaccine by Suppressed Ion Chromatography

The hepatitis B surface antigen manufactured by recombinant DNA technology is extracted from the culture media by density gradient centrifugation using cesium salts. Cesium is considered to be toxic, because it affects active ion transport by blocking potassium channels. The residual trace levels of cesium in hepatitis B vaccine samples are determined by suppressed ion chromatography. Hepatitis B vaccines contain various buffer salts, aluminum-containing adjuvants, proteins and traces of iron. The polyvalent cations (Al³⁺, Fe³⁺) and proteins degrade the chromatographic performance in terms of decreased retention time and poor reproducibility. Different sample preparation approaches were evaluated with the aim of eliminating these foulants: (1) filtration, (2) digestion and (3) digestion-protein precipitation. Quantitative elimination of these foulants was achieved in the digestion-protein precipitation sample clean-up approach. Cesium was separated on the IonPac CS17 column with suppressed conductivity detection. The results of the ion chromatography (IC) method were compared with ICP-MS analysis. The precision of determination was better than 6.5% (relative standard deviation) with a method detection limit of 45 ng mL⁻¹. The expanded uncertainty in the measurement at 95% confidence level (coverage factor 2) is better than 16.3%.

     

Light-induced enantiospecific 4π ring closure of axially chiral 2-pyridones: enthalpic and entropic effects promoted by H-bonding

Nonbiaryl axially chiral 2-pyridones were synthesized and employed for light-induced electrocyclic 4π ring closure leading to bicyclo-β-lactam photoproducts in solution. The enantioselectivity in the photoproducts varied from 22 to 95% depending on the reaction temperature and the ability of the axially chiral chromophore to form intramolecular and/or intermolecular H-bonds with the solvent. On the basis of the differential activation parameters, entropic control of the enantiospecificity was observed for 2-pyridones lacking the ability to form H-bonds. Conversely, enthalpy played a significant role for 2-pyridones having the ability to form H-bonds.     

Electron transfer free radical mechanism in the reactions of arenediazonium cations with grignard reagents

The major pathway in the reactions of arenediazonium cations with certain Grignard reagents is found to involve an electron transfer from the latter to the π-system of the former reactant and radicals are the immediate precursors of the final products.