Structural manipulation of pyrochlores: Thermal evolution of metastable Gd2(Ti1−yZry)2O7 powders prepared by mechanical milling

The structural and microstructural characteristics of metastable Gd₂(Ti_1−yZr_y)₂O₇ powders prepared by mechanical milling have been studied by a combination of XRD and Raman spectroscopy. Irrespective of their Zr content, as-prepared powder phases present an anion-deficient fluorite-type of structure as opposed to the pyrochlore equilibrium configuration obtained for the same solid solution by other synthetic routes. These fluorites are stable versus thermal activation, at least up to temperatures of 800 °C. For the Ti-rich compositions, thermal treatments at higher temperatures facilitate the rearrangement of the cation and anion substructures and the relaxation of mechanochemically induced defects whereas for compositions with high Zr content, the fluorite crystal structure is retained even at temperatures as high as 1200 °C. Interestingly enough, transient pyrochlores showing a very unusual cation distribution were observed during the thermally induced defect-recovery process.     

STS investigations of temperature dependence of Au(1 1 1) surface state energy position

High temperature scanning tunneling spectroscopy (HT-STS) was used to investigate the electronic structure of Au(1 1 1) at different temperatures in the energy range 0-1 eV below the Fermi level. We concentrated on the influence of temperature on the Shockley surface state (SS) appearing on noble metals surface due to a surface projected bulk bang gap in [1 1 1] direction. The influence of temperature on the projected band gap edge (BE) was also investigated. The experiment was carried out in the temperature range 294-580 K. As the result of the experiment a delicate shift of the SS and the BE in direction of the Fermi level was reported.     

General approach for the synthesis of chiral perylenequinones via catalytic enantioselective oxidative biaryl coupling

By using oxygen as the terminal oxidant, copper complexes derived from chiral 1,5-diaza-cis-decalin catalyze the enantioselective oxidative biaryl coupling of highly functionalized naphthols to provide octa- and decasubstituted binaphthalenes with high selectivity (86-90% ee). Products containing very electron-rich naphthalenes were prone to epimerization under the reaction conditions. This epimerization could be suppressed by employing naphthol starting materials with phenol protecting groups that attenuated the electron-rich nature of the naphthalenes. Direct oxidation of the resultant chiral 1,1'-binaphthol framework completed the first asymmetric synthesis of a perylenequinone containing only an axial chirality element.     

Multicenter and multiparticle integrals for explicitly correlated cartesian gaussian-type functions

An analytical derivation of multicenter and multiparticle integrals for explicitly correlated Cartesian Gaussian-type cluster functions is demonstrated. The evaluation method is based on the application of raising operators that transform spherical cluster Gaussian functions into Cartesian Gaussian functions.     

Theoretical analysis of singlet and triplet excited states of nickel porphyrins

Local density and generalized gradient approximation time-dependent density functional methods have been used for calculation of the singlet and triplet excited states of nickel-porphine, Ni-tetraphenyloporphine, and Ni-octaethyloporphyrine. Special attention is paid to metal-ligand transitions and d-d transitions. It is shown that the lowest exited singlet states of the three compounds can be described as a transfer of an electron from the porphine ring to the d(x2-y2) orbital of the nickel atom. On the other hand, the lowest excited triplet state arises from promotion of an electron between two nickel d orbitals, an occupied d(z2) and an empty d(x2-y2). It is proposed that a rapid quenching of the excited singlet states is due to an ultrafast intersystem crossing between 1Eg)and 3Eg or 3B1g states.     

Discretization of the thermal excitation in highly excited matter

In this paper the thermal energy diffusion for quantum particles is described. The quantum heat transport equation is obtained. It is shown that, for a short-time thermal excitation (of the order of the relaxation time), the excited matter response is quantized on the different levels (atomic, nuclear, quark) with quantum thermal energy equalE ^atomic 9 eV,E ^nuclear 7 MeV, andE ^quark 139 MeV.     

Solvated electron in liquid methanol. An example of a statistical species in chemistry

The methods of analysis of the statistical ensembles of trapping sites, before and after electron localization, for electrons in disordered media are surveyed. The review covers the computer-search methods for pre-existing traps in polar matrices, random field theory of disordered polar matrices and the path integral simulations of solvated electron. The common picture provided by all these methods is emphasized: the solvated electron is a unique in chemistry statistical species characterized by statistical distributions of the structural parameters, energy states, reactivity, etc. The numerical examples are provided by the simulations of the trapping sites and the solvated electron in liquid methanol.     

The DTA analysis of amorphous Co-Fe-Si-B alloys

The compositional dependence of the DTA curves was analyzed for Fe_xCo78–_xSi₉B₁₃ metallic glasses. The crystallization temperature were determined. The results suggest that the thermal stability rises with increasing iron content.

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Zusammenfassung An metallischen GlÄsern FexCo78–xSi9B13 wurde die AbhÄngigkeit der DTA-Kurven von der Zusammenfassung untersucht. Den Ergebnissen nach steigt die thermische StabilitÄt mit wachsendem Eisengehalt.

     

Effctive nonadiabatic calculations on the ground state of the HD+ molecule

The nonadiabatic methodology, which is based on an effective elimination of the center-of-mass motion rather than explicit separation achieved by a coordinate transformation, is applied to the ground state of the HD⁺ molecule. The many-body nonadiabatic wave function is generated in terms of explicitly correlated Gaussian functions. The analytical first and second derivatives of the variational functional with respect to the Gaussian exponents are applied in conjunction with the Newton–Raphson optimization method to find the nonadiabatic energy and the ground–wave function. The numerical results are compared with conventional nonadiabatic calculations. © 1995 John Wiley & Sons, Inc.     

Theoretical and experimental studies of asymmetric organozinc additions to benzaldehyde catalyzed by flexible and constrained gamma-amino alcohols

The cis-decalin based gamma-amino alcohols, 1-5, were synthesized, resolved, and employed as catalysts in the addition of organozincs to benzaldehyde. Despite large facial differentiation in the RZn adducts of the ligands, the enantioselectivities were found to be moderate. Transition structure calculations were done using several quantum chemical methods to examine the underlying causes of the selectivity for three gamma-amino alcohols, 1, 2, and 3. The tricyclic mu-oxo (6/4/4), rather than the bicyclic six-membered (6/6), transition structures were found to explain the observed enantioselectivity for 2 and 3. MP2 calculations gave the best correlation to the experimental results compared to B3LYP and HF calculations. The conformational flexibility of the chiral ligands was found to be an important factor in the selectivity.