A new perovskite series based on lanthanum chromite [LaCr1−xMxO3−δ]

A new series of substituted perovskites of the type LaCr1−xMxO3−δ, where M=Cu or Mg have been synthesised by the citrate gel process and characterized by means of powder X-ray diffraction, infrared spectroscopy, selected area diffraction and also by electron paramagnetic resonance spectroscopy. The general powder morphology was also observed using scanning electron microscopy. 40 mole percent substitution of Cr3+ by Cu2+ or Mg2+ have shown to result in single phase perovskite structure. Beyond x=0.5, a new phase has been identified in a narrow compositional range. Effect of Cu and Mg substitution on the sinterability of pure LaCrO3 has also been studied. It is possible to get near theoretically dense materials at a temperature as low as 1200°C in air by copper substitution.

A simple computational model for predicting .pi.-facial selectivity in reductions of sterically unbiased ketones. Relative importance of electrostatic and orbital interactions

Various factore controlling the preferred facial selectivity in the reductions of a number of sterically unbiased ketones have been evaluated using a semiempirical MO procedure. MNDO optimized geometries do not reveal any significant ground-state distortions which can be correlated with the observed face selectivities. Electrostatic effecta due to an approaching reagent were modeled by placing a test negative charge at a fixed distance from the carbonyl carbon on each of the two faces. A second series of calculations was carried out using the hydride ion as a test nucleophile. The latter calculations effectively include orbital interactions involving the u and u* orbitals of the newly formed bond in the reaction. The computed energy differences with the charge model are generally much larger compared to those with the hydride ion. However, both models lead to predictions which are qualitatively consistent with the experimentally determined facial preferences for most of the systems. Thus, electrostatic interactions between the nucleophile and the substrate seem to effectively determine the face selectivities in these molecules. However, there are a few exceptions in which orbital interactions are found to contribute significantly and occasionally reverse the preference dictated by electrostatic effecta. The remarkable succew of the hydride model calculations, in spite of retaining the unperturbed geometries of the substrates, points to the unimportance of torsional effeds and orbital distortions associated with the pyramidalized carbonyl unit in the transition state in most of the substrates considered. Additional experimental results are reported which provide useful calibration for the present computational approach.

A study of chemically prepared small metal clusters in the nonmetallic regime

Small gold clusters [mean diameter (d)[less, similar] 1.4 nm], unlike larger clusters, show a higher Au(4f) binding energy relative to the bulk value and the presence of a conductance gap in tunnelling measurements, just as the molecular cluster compound, Au55(PPh3)12Cl6; small platinum clusters show similar nonmetallic features.

Biorthogonal series method for Oseen type flows

A biorthogonal series method is developed to solve Oseen type flow problems. The theory leads to a new set of eigenfunctions for a specific class of linear non-selfadjoint operators containing the biharmonic one. These eigenfunctions differ from those given earlier in the literature for the biharmonic operator. The method is applied to the problem of thermocapillary flow in a cylindrical liquid bridge of finite length with axial through flow. Flow and temperature distributions are obtained at leading order of an expansion for small surface tension Reynolds number and Prandtl number. Another related problem considered is that of cylindrical cavity flow. Solutions for both cases are presented in terms of biorthogonal series. The effect of axial through flow on velocity and temperature fields is discussed by numerical evaluation of the truncated analytical series. The presence of axial through flow not only convectively shifts the vortices induced by surface forces in the direction of the through flow, but also moves their centers toward the outer cylindrical boundary. This process can lead to significantly asymmetric flow structures.

Bridging the Ruddlesden–Popper and the Dion–Jacobson series of layered perovskites: synthesis of layered oxides, A2–xLa2Ti3–xNbxO10(A = K, Rb), exhibiting ion exchange

Solid solutions of the formula, A2–xLa2Ti3–xNbxO10(A = K, Rb), exist for the range 0[less-than-or-eq]x[less-than-or-eq]1.0, bridging n= 3 members of the Ruddlesden–Popper series (A2La2Ti3O10) and the Dion–Jacobson series (ALa2Ti2NbO10). For 0[less-than-or-eq]x[less-than-or-eq]0.75, the phases possess body-centred structures characteristic of the Ruddlesden–Popper phases, while the x= 1 members are isostructural with KCa2Nb3O10(A = K) and CsCa2Nb3O10(A = Rb). Protonated derivatives, H2–xLa2Ti3–xNbxO10, which are prepared by ion exchange, retain the structural difference of the parent phases. A difference in the Brønsted acidity of the protonated derivatives revealed by intercalation experiments with organic bases seems to be related to this structural difference.

Exotic Physics in the Negative-U, Extended-Hubbard Model for Barium Bismuthates?

We point out possibilities for exotic physics in barium bismuthates, from a detailed study of the negative-U, extended-Hubbard model proposed for these systems. We emphasize the different consequences of electronic and phononic mechanisms for negative U. We show that, for an electronic mechanism, the semiconducting phases must be unique, with their transport properties dominated by charge ± 2e Cooperon bound states. This can explain the observed difference between the optical and transport gaps. We propose other experimental tests for this novel mechanism of charge transport.

K1-xLaxCa2-xNb3O10, a Layered Perovskite Series with Variable Interlayer Cation Density, and LaCaNb3O10, a Novel Layered Perovskite Oxide with No Interlayer Cations

A series of layered perovskite oxides of the formula K1-xLaxCa2-xNb3O10 for 0 < x ≤ 1.0 have been prepared. All the members are isostructural, possessing the structure of KCa2Nb3O10. The interlayer potassium ions in the new series can be ion-exchanged with protons to give H1-xLaxCa2-xNb3O10. The latter readily forms intercalation compounds of the formula (CnH2n+1NH3)1-x LaxCa2-xNb3O10, just as the parent solid acid HCa2Nb3O10. The end member LaCaNb3O10 containing no interlayer cations is a novel layered perovskite oxide, being a n = 3 member of the series An-1BnX3n+1.

Insights into conformational and packing features in a series of aryl substituted ethyl-6-methyl-4-phenyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate

The supramolecular structures of eight aryl protected ethyl-6-methyl-4-phenyl-2-oxo-1,2,3,4-tetrahydropyrimidine- 5-carboxylates have been analyzed to determine the role of different functional groups on the molecular geometry, conformational characteristics and the packing of these molecules in the crystal lattice. Out of these the para fluoro substituted compound on the aryl ring exhibits conformational polymorphism, due to the different conformation of the ester moiety. This behaviour has been characterized using both powder and single-crystal X-ray diffraction, optical microscopy and differential scanning calorimetry performed on both these polymorphs. The compounds pack via the cooperative interplay of strong N-H center dot center dot center dot O=C intermolecular dimers and chains forming a sheet like structure. In addition, weak C-H center dot center dot center dot O=C and C-H center dot center dot center dot pi interactions impart additional stability to the crystal packing.

Squeezed states, photon-number distributions, and U(l) invariance

We study the photon-number distribution in squeezed states of a single-mode radiation field. A U(l)-invariant squeezing criterion is compared and contrasted with a more restrictive criterion, with the help of suggestive geometric representations. The U(l) invariance of the photon-number distribution in a squeezed coherent state, with arbitrary complex squeeze and displacement parameters, is explicitly demonstrated. The behavior of the photon-number distribution for a representative value of the displacement and various values of the squeeze parameter is numerically investigated. A new kind of giant oscillation riding as an envelope over more rapid oscillations in this distribution is demonstrated.

Evolution in the time series of vortex velocity fluctuations across different regimes of vortex flow

Investigations of vortex velocity fluctuation in time domain have revealed a presence of low frequency velocity fluctuations which evolve with the different driven phases of the vortex state in a single crystal of 2H-NbSe2. The observation of velocity fluctuations with a characteristic low frequency is associated with the onset of nonlinear nature of vortex flow deep in the driven elastic vortex state. (C) 2009 Elsevier B.V. All rights reserved.

An examination of the BEBO model with the results of ab initio calculations of a reaction series

The BEBO (bond energy-bond order) model of Johnston and Parr is examined with the results of ab initio MO calculations on a series of metathetic reactions which involve hydrogen transfer. Energies are calculated at the 6-31G**/PMP2 = full//6-31G** level while the bond orders are estimated using the 6-31G** basis set with the geometry optimisation at the single configuration unrestricted Hartree-Fock frame. Our analysis reveals that the bond-order exponent in the BEBO theory is greater than unity for the reaction series and the entropy term becomes implicitly present in the BEBO model.

Bile acid based semi-rigid molecular tweezers

The easily constructed bile acid-based semi-rigid molecular tweezer 2 binds guest 8 in chloroform with an association constant of 83 dm(3) mol(-1).

Observation of asymmetry in U�I characteristics of contacts of the form metal 1�superconductor�metal 2

During experiments carried out to find out a suitable contact metal for electronic components based on high-T(c) superconductor films (Y-Ba-Cu-O), it is observed that there is an asymmetry in the U-I characteristics if the two contacts are made of different metals. The asymmetry is more pronounced if one of the contact metals is aluminium. The asymmetry is lowest if one of the contact metals is silver and the other gold.

On the solution of the equation ut+unux+H(x, t, u)=0

We consider the equation u(t) + u(n)u(x) + H(x, t, u) = 0 and derive a transformation relating it to u(t) + u(n)u(x) = 0. Special cases of the equation appearing in applications are discussed. Initial value problems and asymptotic behaviour of the solution are studied.

Lacunary Fourier series and a qualitative uncertainty principle for compact Lie groups

We define lacunary Fourier series on a compact connected semisimple Lie group G. If f is an element of L-1 (G) has lacunary Fourier series and f vanishes on a non empty open subset of G, then we prove that f vanishes identically. This result can be viewed as a qualitative uncertainty principle.