Stochastic analysis in life office management: applications to large annuity portfolios

The paper deals with the riskiness analysis for a large portfolio of life annuities. By means of the limiting distribution of the present value of the portfolio, in the first part of the paper a model for evaluating the investment and the projection risks is presented. In the second part, with regard to the investment risk's effects, the insolvency risk is measured considering the cumulative probability distribution function of the discounted average cost per policy. Copyright © 2003 John Wiley & Sons, Ltd.     

On the pivot structure for the weighing matrix W(12,11)

In the present article we concentrate our study on the growth problem for the weighing matrix W(12,11) and show that the unique W(12,11) has three pivot structures. An improved algorithm for extending a k × k (0,+,-) matrix to a W(n,n-1), if possible, has been developed to simplify the proof. For the implementation of the algorithm special emphasis is given to the notions of data structures and parallel processing.     

Spectrophotometric Study of Luminol in Dimethyl Sulfoxide–Potassium Hydroxide

The spectrophotometric study of luminol (LH₂) in dimethyl sulfoxide (DMSO), DMSO-water solutions, and alkaline DMSO and DMSO-water solutions has been done, focusing on the effect of the KOH additon on LH₂ absorption and fluorescence properties. The absorption spectra indicate an acid-base equilibrium, and the luminol dianion (L^2–) formation at 3 × 10^–4 – 2.4 × 10^–3 M KOH. The decrease of the fluorescence intensity and the variation of the excitation spectra of LH₂-DMSO-KOH solutions with KOH concentration have been similarly explained. The acid-base process is reversible. The addition of HCl to the solution with 3.0 × 10^–3 M KOH leads to an increase of the fluorescence intensity to its highest value, observed in pure DMSO. The addition of HCl to the LH₂-DMSO solution leads to the decrease of the fluorescence intensity as a result of the LH⁺ ₃ cation formation. In LH₂-DMSO-water, the fluorescence band is shifted from 405 nm to 424 nm and increased in the intensity. In the presence of KOH (in LH₂-DMSO-water-KOH solution) a new band appears, with the maximum at 485 nm and the band at 405 nm decreased. The changes in fluorescence lifetimes also evidence the different chemical species formed.     

Hydrolysis-condensation of tetraethoxysilane in nonparental solvents studied by GC-MS

Gas-chromatography coupled with mass spectrometry was used to investigate the hydrolysis and condensation of tetra-ethoxysilane (TEOS) in nonparental solvents (MeOH and nPrOH). In the presence of nonparental solvents, the reaction that advanced at highest rate is alkoxy group scrambling, that changes the precursor at the molecular level. Subsequent stages of hydrolysis-polycondensation process are essentially determined by the reactivity of the new molecular species formed.     

Mechanism of ferromagnetic coupling in copper(II)-gadolinium(III) complexes

This paper offers the first series of state-of-the-art quantum chemical calculations (CASSCF, CASPT2, MS-CASPT2) and analytical models for the well-known problem of quasi-general ferromagnetic coupling in copper-gadolinium complexes. A system chosen from the chemical report of Costes et al. was taken as prototype. At the CASSCF level, calculated results for the experimental structure reproduced the magnetic coupling constant well (J(calcd)( )()= +7.67 cm(-)(1) vs J(exp)( )()= +7.0 cm(-)(1)). For more insight, the study molecule was further idealized by geometry optimization to C(2)(v)() symmetry. Systematic ab initio computation experiments were designed and performed. Owing to specific problems related to the non-aufbau ground configuration of the [CuL-Gd] complexes, the calculations were conducted in a nonstandard manner. We found that the qualitative mechanism of Kahn, assigned to the electron jump from 3d of Cu(II) to 5d shell of Gd(III), can be presented effectively as the cause of the phenomenon, if CASPT2 MOs are taken as magnetic orbitals. We showed that the ferromagnetic coupling is also matched and magnified by spin polarization effects over the ligand, in line with the early assumption of Gatteschi. To be distinguished from the initial hypothesis of Gatteschi, which assumed the role of 6s AO of Gd(III), we found that one 5d-type AO is actually involved in the polarization scheme. In fact, the Gatteschi and Kahn mechanisms are not mutually contradictory, but are even interconvertible with appropriate changes of the magnetic orbitals. Within C(2)(v)() symmetry of complexes, the ferromagnetic coupling can be qualitatively regarded as the preponderant influence of interaction channels exhibiting orbital orthogonality (four 3d-4f contacts) over the nonorthogonal ones (two 3d-4f contacts). The effective preponderance from ferromagnetic pathways is supported by CASPT2 results. One may explain the generality of Cu(II)-Gd(III) ferromagnetic coupling as being correlated with the large occurrence of approximate pseudo-C(2)(v)() geometry of complexes. The observed orbital regularity is lost in lower symmetries. Thus, the antiferromagnetic exceptions occur when the molecular asymmetry is advanced (e.g., owing to strong chemical nonequivalence of the donor atoms).     

Syntheses, structures, and surface aromaticity of the new carbaalane [(AlH)(6)(AlNMe(3))(2)(CCH(2)R)(6)] (R = Ph, CH(2)SiMe(3)) and a stepwise functionalization of the inner and outer sphere of the cluster

The reaction of the acetylene RC triple bond CH (R = Ph, CH(2)SiMe(3)) with an excess of AlH(3).NMe(3) in boiling toluene leads to the carbaalane [(AlH)(6)(AlNMe(3))(2)(CCH(2)R)(6)] (R = Ph 1, CH(2)SiMe(3) 2) in good yield. Treatment of 2 with BCl(3) under varying conditions gives the chlorinated products [(AlCl)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] 3 and [(AlCl)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(2)Cl)(6)] 4, respectively. The latter clearly demonstrates that the cluster can be stepwise functionalized within the inner and outer sphere. The X-ray single-crystal structures of 1, 2, and 4 have been determined. All compounds have in common that the central core consists of a cluster having eight aluminum and six carbon atoms. The bonding properties in this cluster are described as a new manifestation of three-dimensional surface aromaticity. Each Al(4)C fragment of the cube is formed by four bonds with three electron pairs, thus leading to a strong delocalization of the electrons. A phenomenological modeling using a three-dimensional Hückel scheme with fitted parameters to reproduce the energies from ab initio calculations revealed that the orbital scheme localized at one Al(4)C fragment possesses an orbital sextet with a large HOMO-LUMO gap. This is in line with the criteria of aromaticity. The idea of aromaticity was sustained also by qualitative valence bond reasons enumerating the different resonance structures by means of graph theoretical methods.     

Selective synthesis of isobutanol by means of the Guerbet reaction: Part 2. Reaction of methanol/ethanol and methanol/ethanol/n-propanol mixtures over copper based/MeONa catalytic systems

The synthesis of isobutanol via the Guerbet condensation between methanol and ethanol was studied by using sodium methoxide (MeONa) as soluble basic component and copper-based catalysts as heterogeneous dehydrogenating/hydrogenating metal species. The effect of the nature of the catalyst and the relative amount of its individual components with respect to the reacting alcohols as well as of temperature on productivity and selectivity of the process was investigated. The collected data indicated that the copper chromite/MeONa was more active than Cu-Raney/MeONa system. The reaction was shown to proceed with the formation only of n-propanol and isobutanol. Ethanol conversion up to 61% with selectivity to isobutanol up to 98.4% was obtained. The same catalytic systems were also employed in the reaction of the methanol/ethanol/n-propanol ternary mixture. Again copper chromite/MeONa resulted more active than the Cu-Raney/MeONa system. Finally, experiments were carried out on methanol/n-propanol mixtures in the presence of the copper chromite/MeONa catalytic system by recycling both the recovered solid copper component and the liquid reaction mixture for evidencing eventual copper leaching by MeONa. On the basis of the obtained results it was concluded that in the Guerbet reaction copper chromite works as heterogeneous catalyst.     

Quantum molecular study of sulfur mustard

The sulfur mustard, HD, a chemical warfare agent, has been studied by ab initio quantum molecular computations (HF /6-31G * and 6-31G ) on its various forms (neutral, ethylene sulfonium, and free carbonium ions). The geometries of these molecules have been completely optimized and the minimal energy conformations determined with their associated charge distributions. We discuss these results on electrostatic properties with respect to the mechanism of DNA alkylation by HD and compare them with our previous study of the nitrogen mustard mechlorethamine.     

Spectroscopic study on nystatin conformational modifications generated by its interaction with the solvent

Conformational transformations of the tetraenic nystatin chromophore under the influence of solvents and UV irradiation have been studied by absorption, fluorescence and wide-line NMR spectroscopy.