A new proposal for the discretization of the Griffin—Wheeler—Hartree—Fock equations

A polynomial expansion is proposed as a new way to discretize the Griffin-Wheeler-Hartree-Fock equations of the Generator Coordinate Hartree-Fock method. The implementation of the polynomial expansion in the Generator Coordinate Hartree-Fock method discretizes the Griffin-Wheeler-Hartree-Fock equations through a numerical mesh which is not equally spaced. This procedure makes the optimization of Gaussian exponents in the Generator Coordinate Hartree-Fock method more flexible and more efficient. The results obtained with the polynomial expansion for atomic Hartree-Fock energies show this technique is very powerful when employed in the design of compact and high accurate Gaussian basis sets used in ab initio non-relativistic (Hartree-Fock) and relativistic (Dirac-Fock) calculations.     

THE PHOTOREDUCTION OF METHYLENE BLUE BY ARYLAMINOMETHANE-SULFONATES

Abstract— The photoreduction of methylene blue in the presence of arylaminomethanesulfonates (RAMS = RC₆H₄NHCH₂SO₃Na) was studied by laser and conventional flash photolysis. These compounds quenched the methylene blue triplet deviating from a normal Stern-Volmer behaviour. For low quencher concentrations, a Rehm-Weller relationship was found between the k _q's and the DL G 's obtained for the electron transfer reactions. The lack of further quenching at higher [RAMS] is ascribed to the formation of a ground state ion pair between the dye and the anionic quencher which, on excitation, forms a triplet state unable to under go electron transfer for steric reasons. A second order decay rate constant was found for the semireduced species (MB') ( ca. 5 × 10⁹ M _-1 s_-1, independent of the RAMS used) and is attributed to a proton transfer from the radical zwitterion (RC₆H₄NH CH₂SO₃⁻) to MB. The overall dependence on the substituent of the bleaching observed by continuous irradiation follows the triplet behaviour.     

A study of the adsorption of the amphiphilic penicillins cloxacillin and dicloxacillin onto human serum albumin using surface tension isotherms

The interaction of human serum albumin (HSA) with two structurally similar anionic amphiphilic penicillins, cloxacillin and dicloxacillin, at 25 °C has been examined by surface tension measurements under conditions at which the HSA molecule was positively (pH 4.5) or negatively charged (pH 7.4). Measurements were at fixed HSA concentrations (0.0125 and 0.125% w/v) and at drug concentrations over a range including, where possible, the critical micelle concentration (cmc). Interaction between anionic drugs and positively charged HSA at pH 7.4 resulted in an increase of the cmc of each drug as a consequence of its removal from solution by adsorption. Limited data for cloxacillin at pH 4.5 indicated an apparent decrease of the cmc in the presence of HSA suggesting a facilitation of the aggregation by association with the protein. Changes in the surface tension-log (drug concentration) plots in the presence of HSA have been discussed in terms of the adsorption of drug at the air-solution and protein-solution interfaces. Standard free energy changes associated with the micellization of both drugs and their adsorption at the air-solution interface have been calculated and compared.     

CARBOXYLATED ZINC-PHTHALOCYANINE, INFLUENCE OF DIMERIZATION ON THE SPECTROSCOPIC PROPERTIES. AN ABSORPTION, EMISSION, AND THERMAL LENSING STUDY

Monomer and dimer absorption and emission spectra, and dimerization constants are reported for the diamide of the zinc-tetracarboxyphthalocyanine in pure dimethylformamide (DMF) and in H₂O/DMF mixtures at room temperature. The dimerization constant increases steadily with the water content. The monomer absorption Q-band is insensitive to the solvent composition, whereas dimer spectra show great variations with the water content. Stationary emission measurements show that fluorescence originates exclusively from the monomers. The fluorescence spectrum as well as its absolute fluorescence quantum yield, measured by steady-state thermal lensing, are also insensitive to the solvent composition. The thermal lensing method is discussed for the case of two absorbing species in equilibrium.     

A MIXED CONTROL PROBLEM OF THE MANAGEMENT OF NATURAL RESOURCES

In this paper, we study the optimal solutions of a model of natural resource management which allows for both impulse and continuous harvesting policies. This type of model is known in the literature as mixed optimal control problem. In the resource management context, each type of control represents a different harvesting technology, which has a different cost. In particular, we want to know when the following conjecture made by Clark is an optimal solution to this mixed optimal control problem: if the harvesting capacity is unlimited, it is optimal to jump immediately to the steady state of the continuous time problem and then to stay there. We show that under a particular relationship between the continuous and the impulse profit function, the conjecture made by Clark is true. In other cases, however, it is either better to use only continuous control variables or to jump to resource levels which are smaller than the steady state and then let the resource grow back to the steady state. These results emphasize the importance of the cost functions in the modeling of natural resource management.     

Searching for quarks: a quantum chemical assisted approach

The evidence for quarks as the basic blocks of matter come only from very expensive experiments, performed in very large particle accelerators. An alternative method of detection is to look for changes in spectroscopic properties that could be influenced by fractionally charged nuclei formed with the ‘wrong’ number of quarks. Although this proposal has already been made by many authors, they were not able to provide feasible and easily interpretable experiments to detect quarks in matter. In this paper, we present the results of configuration interaction (CI) calculations for the transition energies and optical oscillator strengths associated with inner shell electronic spectra of molecular nitrogen made of fractionally charged nuclei. It is shown that these bands can be used as fingerprints characterizing the presence of quarks in matter.     

POLYMER BOUND PYRROLE COMPOUNDS–VI. PHOTOPHYSICAL PROPERTIES OF MONOMERIC MODELS FOR POLYSTYRENE-BOUND PORPHYRINS

Abstract— Several porphyrin esters used as models for polystyrene-bound porphyrins have been prepared and their excited states have been studied by laser flash photolysis, IR phosphorescence of singlet molecular oxygen, O₂(¹Δ_g), and steady-state fluorescence. The photophysical properties of the porphyrin esters in solution are affected by the presence of nitro group(s) in the chain. In this case, an important decrease in φ_f, φ_T and φ_δ (to ca 0.7–0.4 of the value for the parent dimethyl ester) is observed. This is mainly due to intramolecular electron-transfer quenching [by the nitro group(s)] of the first excited singlet state of the porphyrin. The thermodynamic feasibility of this deactivation pathway has been confirmed polarographically. Quenching of the porphyrin triplet state and of O₂(¹Δ_g) by the nitro groups is negligible. The present conclusions explain also the results obtained previously for the photooxidation of bilirubin sensitized by the parent insoluble polystyrene-bound porphyrins. In that case the photooxidation rates were correlated directly with the quantum yield of O₂(¹Δ_g) production by the sensitizer. The consequences of these results for the use of polystyrene-bound porphyrins in sensitized photooxidation processes are discussed.