Chaos in classical cosmology (II)

We present a new dynamical calculation about the Friedman-Robertson-Walker universe considered as an autonomous Hamiltonian. The time evolution of this Hamiltonian presents numerical instabilities so we apply a symplectic integration via infinitesimal canonical transformations of the phase space time evolution that preserves the Poincaré invariant. In this way, we have also obtained a sensitive improvement in the accuracy of the Hamiltonian constraint, as well as in the computing time. We confirm our previous results; in a spatially closed universe, the route to chaos is reached by sucessive breakage of the resonant tori due to the action of 11 resonances.     

On the layering transition of an SOS surface interacting with a wall. II. The Glauber dynamics

We continue our study of the statistical mechanics of a 2D surface above a fixed wall and attracted towards it by means of a very weak positive magnetic fieldh in the solid on solid (SOS) approximation, when the inverse temperature is very large. In particular we consider a Glauber dynamics for the above model and study the rate of approach to equilibrium in a large cube with arbitrary boundary conditions. Using the results proved in the first paper of this series we show that for allh(h _k+1 ^* ,h _k ^* ) ({h _k ^* } being the critical values of the magnetic field found in the previous paper) the gap in the spectrum of the generator of the dynamics is bounded away from zero uniformly in the size of the box and in the boundary conditions. On the contrary, forh=h _k ^* and free boundary conditions, we show that the gap in a cube of sideL is bounded from above and from below by a negative exponential ofL. Our results provide a strong indication that, contrary to what happens in two dimensions, for the three dimensional dynamical Ising model in a finite cube at low temperature and very small positive external field, with boundary conditions that are opposite to the field on one face of the cube and are absent (free) on the remaining faces, the rate of exponential convergence to equilibrium, which is positive in infinite volume, may go to zero exponentially fast in the side of the cube.Work partially supported by grant SC1-CT91-0695 of the Commission of European Communities.     

Solid-state supramolecular organization, established directly from powder diffraction data, and photoluminescence efficiency of rigid-core oligothiophene-S,S-dioxides

The "rigid-core" material 3,5-dimethyl-2,3'-bis(3-methylthiophene)-dithieno[3,2-b:',3'-d]thiophene-4,4-dioxide (DTTOMe4) has the highest photoluminescence ever reported for thiophene-based molecules in the solid state. We report the structure of this material, determined directly from powder X-ray diffraction data using the Genetic Algorithm method for structure solution, followed by Rietveld refinement, and the structural properties are discussed in relation to the structures of the corresponding subsystems DTTO and DTTOMe. While the crystal structures of the latter compounds contain cofacial dimers, the crystal structure of DTTOMe4 comprises layers of molecules aligned in an antiparallel fashion. Intermediate neglect of differential overlap with single configuration interaction (INDO/SCI) calculations on the intermolecular interactions in the three crystal structures show that the different solid-state photoluminescence efficiencies of DTTOMe4, DTTOMe, and DTTO cannot be correlated with the different types of dipole-dipole alignment in the solid state. Instead, photoluminescence efficiencies correlate well with the rate of formation of nonradiatively decaying charge-transfer pairs upon photoexcitation. Because of larger intermolecular distances in DTTOMe4, the photoluminescence is less effectively quenched by charge-transfer processes than in DTTOMe and DTTO.     

Charge transfer in FeO: a combined molecular-dynamics and ab initio study

Molecular-dynamics simulations and ab initio electronic structure calculations were carried out to determine the rate of charge transfer in stoichiometric wustite (FeO). The charge transfer of interest occurs by II/III valence interchange between nearest-neighbor Fe atoms, with the Fe(III) constituting a "hole" electronic defect. There are two possible nearest-neighbor charge transfers in the FeO lattice, which occur between edge-sharing or corner-sharing FeO(6) octahedra. Molecular-dynamics simulations predict charge-transfer rates of 3.7 x 10(11) and 1.9 x 10(9) s(-1) for the edge and corner transfers, respectively, in good agreement with those calculated using an ab initio cluster approach (1.6 x 10(11) and 8.0 x 10(8) s(-1), respectively). The calculated rates are also similar to those along the basal and c-axis directions in hematite (alpha-Fe(2)O(3)) determined previously. Therefore, as is the case for hematite, wustite is predicted to show anisotropic electrical conductivity. Our findings indicate that a rigid-ion model does not give acceptable results, thus showing the need to account for the change in polarizability of the system upon charge transfer. Our model achieves this by using a simple mechanical shell model. By calculating the electronic coupling matrix elements for many transition state configurations obtained from the molecular-dynamics simulations, we found evidence that the position of the bridging oxygen atoms can greatly affect the amount of electronic coupling between the donor and acceptor states. Finally, we address the effect of oxygen vacancies on the charge transfer. It was found that an oxygen vacancy not only creates a driving force for holes to transport away from the vacancy (or equivalently for electrons to diffuse toward the vacancy) but also lowers the free-energy barriers for charge transfer. In addition, the reorganization energy significantly differed from the nondefective case in a small radius around the defect.     

Photodegradation of Polychlorinated Dibenzo-p-dioxins in Liquid Samples by Near UV Light Irradiation

Photodegradation of 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD) in hexane solution was studied under controlled near-UV light exposure in the spectral region from 325 to 269 nm. GC-MS was used to detect the amount of unreacted dioxin and to characterize the relevant degradation products. Irradiation experiments carried out at a constant light energy (700 mJ) showed that the percentage of 1,2,3,4-TCDD left in the solution after irradiation changed from about 55 to 75%, with a minimum of 55% at 310 nm. Further irradiation experiments carried out at two wavelengths, namely 310 and 269 nm, and light energy ranging from 0 to 4000 mJ, showed that the photodegradation reaction of the TCDD always followed a pseudo-first-order kinetic, with a rate constant of 8 × 10⁻⁴and 5 × 10⁻⁴mJ⁻¹, respectively. These experiments also showed that trichloro- and dichloro-dibenzo-p-dioxins were produced with less than 15% of the initial quantity of TCDD, leading to the conclusion that the dechlorination process is a minor photolysis pathway.     

A new algorithm to evaluate bielectronic integrals with 1s Slater‐type orbitals obtained by the integral transforms

This article presents a variation of the integral transform method to evaluate multicenter bielectronic integrals (12|34), with 1s Slater‐type orbitals. It is proved that it is possible to define, out of the expression of (12|34) given by the integral transform method, a function F(q) that has the property of having a unique Q, such that F(Q) = (12|34). Therefore, F(q) may be used to calculate (12|34). It is shown that the evaluation of F(Q) turns out to be simpler than the three‐dimensional integral involved in the calculation of (12|34), and an algorithm is presented to calculate Q. The results show that relative errors on the order of 10^?3 or lower are obtained very efficiently. In addition, it is shown that the proposed algorithm is very stable. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

Electronic structure of BeH2

Nonorthogonal single‐configuration and multiconfiguration ab initio calculations are carried out on the BeH₂ molecule in its equilibrium (D_∞h) geometry, using a highly optimized even‐tempered Slater‐type orbital (STO) basis set. The results are used as a basis for a discussion of the electronic structure of the molecule in modern‐VB terms. A value of R_e = 1.329 Å is obtained. Values are also obtained for the symmetric‐stretch harmonic frequency (2053 cm^?1), electric quadrupole moment (?5.60 Buckingham), and nuclear quadrupole coupling constants (?3.59 MHz for ⁹Be and 0.0915 MHz for ²H). © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Molecular dynamics investigation of ferrous-ferric electron transfer in a hydrolyzing aqueous solution: calculation of the pH dependence of the diabatic transfer barrier and the potential of mean force

We present a molecular model for ferrous-ferric electron transfer in an aqueous solution that accounts for electronic polarizability and exhibits spontaneous cation hydrolysis. An extended Lagrangian technique is introduced for carrying out calculations of electron-transfer barriers in polarizable systems. The model predicts that the diabatic barrier to electron transfer increases with increasing pH, due to stabilization of the Fe3+ by fluctuations in the number of hydroxide ions in its first coordination sphere, in much the same way as the barrier would increase with increasing dielectric constant in the Marcus theory. We have also calculated the effect of pH on the potential of mean force between two hydrolyzing ions in aqueous solution. As expected, increasing pH reduces the potential of mean force between the ferrous and ferric ions in the model system. The magnitudes of the predicted increase in diabatic transfer barrier and the predicted decrease in the potential of mean force nearly cancel each other at the canonical transfer distance of 0.55 nm. Even though hydrolysis is allowed in our calculations, the distribution of reorganization energies has only one maximum and is Gaussian to an excellent approximation, giving a harmonic free energy surface in the reorganization energy F(DeltaE) with a single minimum. There is thus a surprising amount of overlap in electron-transfer reorganization energies for Fe(2+)-Fe(H2O)6(3+), Fe(2+)-Fe(OH)(H2O)5(2+), and Fe(2+)-Fe(OH)2(H2O)+ couples, indicating that fluctuations in hydrolysis state can be viewed on a continuum with other solvent contributions to the reorganization energy. There appears to be little justification for thinking of the transfer rate as arising from the contributions of different hydrolysis states. Electronic structure calculations indicate that Fe(H2O)6(2+)-Fe(OH)n(H2O)(6-n)(3-n)+ complexes interacting through H3O2- bridges do not have large electronic couplings.     

Multielemental analysis of food and agricultural matrixes by inductively coupled plasma-mass spectrometry

The suitability of quadrupole inductively coupled plasma-mass spectrometry (ICP-MS) for multielemental analysis of food following microwave closed vessel digestion of samples was evaluated in relation to analytical challenges presented by some major food and agricultural matrixes. Fifteen key analytes (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Se, Sn, V, Zn) were determined in 9 reference materials representative of 3 major groups of staple foods (cereals, seafood, and meat). For all measurements, the method of external calibration was used and Rh was selected as internal standard. Matrix-induced interferences were evaluated for each material, and suitable methods to overcome them were applied. Spectral interferences caused by C, Cl, and Ca content of digestates were quantitated and corrected by entering a simple system of mathematical correction equations into the instrument software before each analytical run. Full mastering of interferences together with adoption of a series of measures to control the reliability of analytical measurements produced accurate results for all the analytes. A standard analytical protocol is outlined for the benefit of both research and routine high-throughput laboratories that perform ICP-MS analyses of food.     

Reduction of cyclohexanone 2-nitrophenylhydrazone. Formation of cyclohexane-3-spiro-3,4-dihydro-1,2,4-benzotriazine

The structure of compound C₁₂H₁₅N₃, obtained by Perkin and Riley in 1923, through the reduction of cyclohexanone 2-nitrophenylhydrazone, was reexamined. This compound, considered originally as 3,4-cyclotetramethylene-4,5-dihydro-1,2,5-benzotriazepine (I) and later as 2-aminophenylazocyclohexene (II), is now defined through the nmr spectrum and chemical behaviour as cyclohexane-3-spiro-3,4-dihydro-1,2,4-benzotriazine (V). It is formed by spontaneous oxidation of the cyclic form of cyclohexanone 2-aminophenylhydrazone (namely, cyclohexane-3-spiro-1,2,3,4-tetrahydro-1,2,4-benzotriazine) obtained through amino group addition on the hydrazone double bond.