On a semiclassical interpretation of inter- and intramolecular interactions

The semiclassical models considered here are composed by charge distributions coming from ab initio quantum-mechanical calculations on actual molecular systems. These charge distributions interact with one another according to the laws of classical electrostatics. This article describes some results of a systematic examination of the performances of this model in a variety of cases, with the aim of putting in evidence the usefulness and the limits of this inherently approximate representation of chemical interactions. Intermolecular interactions are examined first; the test cases are interactions of neutral molecules with H⁺, Li⁺, and C1^?, and the formation of H-bonded complexes. Attention is paid mainly to the energetics of the processes; each interacting molecule is considered as a unique entity and classical molecular reactivity indexes (electrostatic potential V, polarization term P) are introduced to compute the interaction energy, to interpret the details of the interaction process, and then to elaborate on less expensive computational procedures. Intramolecular interactions are considered. Attention is paid to the question of defining chemical groups starting from SCF molecular wavefunctions. The transferability and conservation degree of groups derived from localized orbitals of actual molecules is examined in detail, taking as tests their ability to reproduce charge distribution, one-electron observables, and energy. The effect of classical fields on these groups is then examined, taking into consideration external fields originated either by a point charge or by a solvent, and internal fields deriving from substitution of chemical groups. The intergroup analysis is then extended to the case of bimolecular reaction acts by considering the whole system as a supermolecule. Approximate computational procedures able to reproduce the main features of these interactions are proposed and tested. All through the article the performances of the classical models are compared with ab initio SCF calculations (mainly of low or intermediate quality).     

The synthesis,characterization and reactions of a binuclear tetramethylplatinum(IV) complex

Reaction of excess MeLi and MeI with [PtCl₂SMe₂)₂] gives the first binuclear tetramethylplatinum(IV) complex [Pt₂Me₈(μ-SMe₂)₂]. The characterization of this complex, and its reactions with donor ligands to give cis-[PtMe₄L₂] (L₂ = Ph₂PCH₂PPh₂, Ph₂PCH₂CH₂PPh₂, 2,2′-bipyridyl, 1,10-phenanthroline or L = PMe₂Ph, PMePh₂) are described.     

Microwave enhanced solvent-free synthesis of a library of quinoline derivatives

A minilibrary of 12 quinoline derivatives was synthesized in the presence of 0.1-0.5 equiv. of diphenylphosphate without any solvents. Each compound was obtained with high yield in 4 min of microwave irradiation.     

Decision analysis models in reinsurance

Decision analysis models are developed and illustrated for the reinsurance (risk transfer) decisions made by insurance companies. Decision analytic models were found to be useful tools both for structuring multistage reinsurance decisions and for comparing alternative options. The insurer is faced with many possible choices involving reinsurance type and extent, and an expected utility model provided insight both as a screening device and as an evaluation criterion. Decision analytic models appeared to be superior to other approaches such as mean/variance and risk of ruin models both because of their flexibility and their more comprehensive treatment the important elements of the decision, namely the complete claims distribution, the cost of reinsurance and the insurer's risk attitude.     

On the conformation of bipyridine dications and cation radicals

Ab initio STO-3G calculations with partial geometry optimization were performed to determine the conformational structure of 2,2′- and 4,4′-bipyridine dications and their cation radicals. The results suggest a considerably twisted conformation for the dications, whereas the corresponding radical cations are nearly planar. Reasons for the structure differences are discussed and related to the herbicidal action of these compounds.     

A thermally stable polymer molecular composite

A molecular composite of rigid-rod poly(p-phenylene benzobisthiazole) and flexible-coil poly(benzimidazobenzophenantroline) has been prepared, characterized, and shown to be thermally stable to at least 300°C. These results suggest that stable miscible blends of rodlike and coil-like polymers can be prepared by controlling the glass transition temperature of the flexible-coil polymer. © 1995 John Wiley & Sons, Inc.     

Synthesis and characterization of La0.9Sr0.1Ga0.8Mg0.2O3-δ electrolyte for intermediate temperature solid oxide fuel cells (ITSOFC)

Experimental investigations on new materials for application as electrolyte in electrolyte supported planar Intermediate Temperature Solid Oxide Fuel Cells (ITSOFC) operating below 800 °C is in progress at our laboratory. Sr and Mg doped Lanthanum gallate (LSGM) powder was prepared by glycine — nitrate combustion method. The prepared LSGM powder is relatively finer than that prepared through other techniques such as solid-state reaction. The measurements comprising XRD, particle size, density, TGA/DTA were made. Thin sections of circular pellets were fabricated and annealed at different temperatures ranging between 1000 and 1300 °C. The sintering behaviour of LSGM was investigated to obtain information on the densification factor, relative percentage shrinkage/expansion in volume, while annealing and the resulting apparent porosity values. Bismuth oxide is found to be an effective sintering aid in general. So the effect of bismuth oxide addition on LSGM was investigated through sintering studies, XRD, TGA/DTA, SEM and conductivity measurements. The results obtained on LSGM with and without bismuth oxide addition are discussed with respect to the requirement of an electrolyte for ITSOFC applications. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Observation of surface and bulk plasmons in semiconductor superlattices

We report far infrared measurements of oblique incidence power reflectivity and attenuated total reflection (ATR) on multiply Si δ-doped GaAs samples. The reflectivity spectrum in s-polarisation probes the in-plane component of the superlattice dielectric function, and is sensitive to the overall 3D electron density. The p-polarisation spectrum, however, also probes the out-of-plane component, resulting in an extra mode which is sensitive to the distribution of free electrons between wells and barriers. The p-polarisation ATR spectrum shows surface modes which are also sensitive to this distribution. The results are compared with a bulk slab model of the dielectric function.     

An analysis of the interaction energy in some SN2 reactions

The interaction energy between an incoming group X^– and the substrate CRH₂Y at the geometry of the transition state (TS) for bimolecular nucleophilic substitution reactions (with X, Y, and R equal to H and F) has been subjected to decomposition according to the Morokuma scheme. The influence of the basis set and of the geometry chosen for the TS is examined. The results bring out regular trends in the different terms of the decomposition along the whole set of reactions, but they are not sufficient to give a rationale of the energetic factors involved in these reactions.     

Properties of dysprosium-doped gallium lanthanum sulfide fiber amplifiers operating at 1.3 microm

In light of recent progress in the fabrication of gallium lanthanum sulfide (GaLaS) fibers, we have modeled the performance of dysprosium-doped GaLaS fiber amplifiers operating at 1.3mum . Based on experimental data, we find that the incorporation of a codopant (terbium) in the fiber core significantly shortens the optimum amplifier length from >30 m to ~3 m . Such a device may be practical, given the fiber losses currently achieved in GaLaS fibers.