High pressure spectroscopy of chromium doped LiTaO3 crystals

Abstract

The effect of pressure on the luminescence spectrum of the weak field system Cr³⁺ : LiTaO₃ is presented. By using pressure to induce a low to high crystal field strength transition, we demonstrate the ability of pressure to identify distinct dopant bonding environments in luminescent materials.     

On the existence of more positive solutions of periodic bvps with singularity

We consider Periodic boundary value problems for ordinary second order differential equations of the form u′′=f(t,u,u′), Where f satisfies the (local) Carathéodory conditions and can have a singularity in the second variable.Writing our problem in an operator can be computed on. These sets are not convex, in general. Using the degree theory we get at least one fixed point of the operator at each such set which leads to the existence and localization of more solutions of the related Periodic boundary value problem. Our results are based on the generalized lower and upper functions method from Rach?nková and Tvrdý[15].     

Antiferroelectric phase transitions in single crystals PbZrO3:Sn revisited

This paper is a review of earlier results which have been completed with recent investigations on the nature and sequence of phase transitions evolving in the antiferroelectric PbZr_1–xSn_xO₃ single crystals (0 < x < 0.35). It was found that these crystals undergo several first-order phase transitions. To investigate these transitions, five experimental methods were used to characterize the crystal properties: birefringence, Raman light scattering, dielectric, thermodynamic and electromechanical methods, and the atomic force microscopy-piezoresponse force microscopy (AFM-PFM) method to focus also on nanoscale properties. Temperature dependencies have been tentatively measured in a wide range, including a region above T_C, where precursor dynamics is observed in the form of non-centrosymmetric regions existing locally in crystal lattices.

New experimental data (Raman light scattering and PFM) are presented mainly to revise the phase diagram and, at the same time, to complement other studies on the problem of pre-transitional effects. The phase transition mechanism in PbZr_1–xSn_xO₃ is discussed taking into account the incommensurability of crystal lattices, ferroelastic behavior of multicell cubic phases, electric field influence on antiferroelectric to ferroelectric transformation, and flexoelectric effect.     

Application of different thermal analysis techniques for the evaluation of petroleum source rocks

In the paper, various laboratory pyrolytic methods were used to evaluate selected petroleum source rocks. The methods used are: Rock–Eval pyrolysis, Py–GC pyrolytic technique and TG/DTG/DSC. The experiments of the last method were performed according to three different procedures. Each of them provided different, specific data. The selected rock sample material was diversified in terms of stratigraphical position, structural unit and place of collection (outcrop or borehole). Based on the Rock–Eval analysis results, kerogen in samples can be classified as type II. Additional information on the quality of pyrolysis products was obtained from the Py–GC analysis. Thanks to the combination of the all three implemented pyrolytic techniques, the quality of the generation potential of the source rocks can be evaluated in details. In some samples, the oxidation and pyrolysis of organic matter occur in two stages, what is the evidence of the complex nature of the organic substance. The maximum of pyrolysis reaction is detected by TG/DTG measurement in the range of temperature from 450 to 580 °C, depending on the maturity of organic matter. The maturity level increases with the rock stratigraphic position. The proportions of loss in mass observed in respective stages of pyrolysis in course of TG/DTG experiment are in correspondence with the observations of the released fractions in the Py–GC analysis. The Carpathian Menilite shales could be classified as source rocks with high oil generation potential. Also, the Lower Silurian and Ordovician shales are characterized by high oil-producing potential with a lower content of mineral matter. Cambrian rocks show a different character and gas-prone generation potential.

     

DFT B3LYP/6-311+G* calculation study of a new nonclassical mechanism of electrophilic functionalization of aromatic C–H bond via aryl cation formation

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Weak interactions in furan dimers

Dimers of furan, 2,3-dihydrofuran, 2,5-dihydrofuran and tetrahydrofuran were investigated with the use of theoretical methods to determine the interactions that keep the molecules together. The QTAIM and NCI methods confirmed that for furan dimers the C–H?O hydrogen bond and stacking interactions can form the dimers with similar energy. For 2,3-dihydrofuran, 2,5-dihydrofuran and tetrahydrofuran, the decisive mechanism of dimer formation is the stacking interaction between the furan rings.     

Maximum weight edge-constrained matchings

Practical questions arising from (for instance) biological applications can often be expressed as classical optimization problems with specific, new features. We are interested here in the version of the maximum weight matching problem (on a graph G) obtained by (1) defining a set F of pairs of incompatible edges of G and (2) asking that the matching contains at most one edge in each given pair. Such a matching is called an odd matching. The graph T(F)=(V_F,F), where V_F is the set of edges of G occurring in at least one pair of F, is called the trace-graph of G and F.We motivate the introduction of the maximum weight odd-matching (abbreviated as Odd-MWM) problem and study its complexity with respect to two parameters: the type of graph G and the graph class T to which T(F) belongs.Our contribution includes:

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A proof that Odd-MWM is NP-complete for 3-degree bipartite graphs when T(F) is a matching (i.e. when T is the class of 1-regular graphs), even if the weight function is constant.

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A proof that Odd-MWM is NP-complete (for 3-degree bipartite graphs as well as for any larger class) if and only if T is a class of graphs with unbounded induced matching. Otherwise, Odd-MWM is polynomial.

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A (Δ(T(F))+1)-approximate algorithm for Odd-MWM on general graphs. This algorithm becomes a χ(T(F))-approximate algorithm when the graph class T admits a polynomial algorithm for minimum vertex coloring.

     

The shape of the potential energy curves for NHN(+) hydrogen bonds and the influence of non-linearity

The potential energy curves for proton motion in NHN(+) hydrogen bonds have been calculated to investigate whether different methods of evaluation give different results: for linear H bonds most curves calculated along the NH direction are, as expected, identical with those along NN; for intramolecular H bonds it is very important to take into account the non-linearity and the potential energy curve calculated along the NH direction can be very far from the curve correctly describing the proton transfer. Other factors which influence the proton-transfer process are steric hindrance and presence of anions which modify the proton motion. In the analysis of the proton transfer process it is very important to take changes in the structure of the rest of the molecule into account, which is connected with exchange of energy with the surroundings. Comparison of adiabatic and non-adiabatic curves shows that they are significantly different for very bent hydrogen bonds and for hydrogen bonds with steric constraints for which the proton transfer process must be accompanied with relaxation of the whole molecule. Comparison of the potential-energy curves for compounds with very short H bonds emphasizes that the term 'strong H bond' needs to be qualified. For intermolecular H bonds shortening of the bond is connected with linearization. But for intramolecular H bonds the NN distance cannot be used as the only measure of H bond strength.     

Temperature-dependent single-crystal neutron diffraction study of the strong OHN hydrogen bond in pyridinium 2,4-dinitrobenzoate

The structure of pyridinium 2,4-dinitrobenzoate was studied by neutron diffraction at 300, 270, 240, 210, 180, 150, 120, 90, 60, and 30 K. With temperature change, the O...H bond length changes from 1.403(10) A at 300 K to 1.424(4) A at 30 K. The proton shifts in the hydrogen bridge toward the acceptor nitrogen atom. Temperature-dependent changes in the strong OHN hydrogen bond were analyzed by using both the neutron structure and the atom-in-molecule approach. The results are compared with those for other strong OHN hydrogen bonds.     

Open cellular reactive porous membranes from high internal phase emulsions

High internal phase emulsions (HIPEs) incorporating styrene, 4-vinylbenzyl chloride, divinylbenzene and ethylhexyl acrylate were applied to prepare reactive, cross-linked porous membranes with open cellular architecture and thicknesses between 30 and 500 mum.