Theory of the non-planar peptide unitstar, open

By means of CNDO/2 calculations on N-methyl acetamide, it is shown that the state of minimum energy of the trans-peptide unit is a non-planar conformation, with the NH and NC2α bonds being significantly out of the plane formed by the atoms C1α, C′, O and N.

Unusual effects of anisotropic bonding in Cu(II) and Ni(II) oxides with K2NiF4 structure

Geometric constraints present in A2BO4 compounds with the tetragonal-T structure of K2NiF4 impose a strong pressure on the B---OII---B bonds and a stretching of the A---OI---A bonds in the basal planes if the tolerance factor is t congruent with RAO/√2 RBO < 1, where RAO and RBO are the sums of the A---O and B---O ionic radii. The tetragonal-T phase of La2NiO4 becomes monoclinic for Pr2NiO4, orthorhombic for La2CuO4, and tetragonal-T′ for Pr2CuO4. The atomic displacements in these distorted phases are discussed and rationalized in terms of the chemistry of the various compounds. The strong pressure on the B---OII---B bonds produces itinerant σ*x2−y2 bands and a relative stabilization of localized dz2 orbitals. Magnetic susceptibility and transport data reveal an intersection of the Fermi energy with the d2z2 levels for half the copper ions in La2CuO4; this intersection is responsible for an intrinsic localized moment associated with a configuration fluctuation; below 200 K the localized moment smoothly vanishes with decreasing temperature as the d2z2 level becomes filled. In La2NiO4, the localized moments for half-filled dz2 orbitals induce strong correlations among the σ*x2−y2 electrons above Td reverse similar, equals 200 K; at lower temperatures the σ*x2−y2 electrons appear to contribute nothing to the magnetic susceptibility, which obeys a Curie-Weiss law giving a μeff corresponding to S = 1/2, but shows no magnetic order to lowest temperatures. These surprising results are verified by comparison with the mixed systems La2Ni1−xCuxO4 and La2−2xSr2xNi1−xTixO4. The onset of a charge-density wave below 200 K is proposed for both La2CuO4 and La2NiO4, but the atomic displacements would be short-range cooperative in mixed systems. The semiconductor-metallic transitions observed in several systems are found in many cases to obey the relation Ea reverse similar, equals kTmin, where varrho = varrho0exp(−Ea/kT) and Tmin is the temperature of minimum resistivity varrho. This relation is interpreted in terms of a diffusive charge-carrier mobility with Ea reverse similar, equals ΔHm reverse similar, equals kT at T = Tmin.

Einstein relation in n-i-p-i and microstructures of nonlinear optical, optoelectronic and related materials: Simplified theory, relative comparison and suggestions for an experimental determination

We investigate the Einstein relation for the diffusivity-mobility ratio (DMR) for n-i-p-i and the microstructures of nonlinear optical compounds on the basis of a newly formulated electron dispersion law. The corresponding results for III-V, ternary and quaternary materials form a special case of our generalized analysis. The respective DMRs for II-VI, IV-VI and stressed materials have been studied. It has been found that taking CdGeAs2, Cd3As2, InAs, InSb, Hg1−xCdxTe, In1−xGaxAsyP1−y lattices matched to InP, CdS, PbTe, PbSnTe and Pb1−xSnxSe and stressed InSb as examples that the DMR increases with increasing electron concentration in various manners with different numerical magnitudes which reflect the different signatures of the n-i-p-i systems and the corresponding microstructures. We have suggested an experimental method of determining the DMR in this case and the present simplified analysis is in agreement with the suggested relationship. In addition, our results find three applications in the field of quantum effect devices.

2-Thioacetamido thiazole as an ambidentate ligand. Complexes of Zn(II), Cd(II), Hg(II) and Cu(I)

Metal complexes of thiazoles have been studied in recent years[I-3] because of their biochemical importance[4,5]. However, data on metal complexes of thiazole derivatives containing another coordinating function are limited[2]. We have synthesized and examined the donor characteristics of a new ligand, 2-thioacetamide thiazole (TATZ)(I) towards chlorides and bromides of Zn(II), Cd(II), Hg(II) and Cu(I). The presence of four potential donor atoms and extensive charge delocalization should render TATZ a versatile ligand.

An inhomogeneity problem in couple stress theory

Using Hilbert theory and Mindlin's couple stress theory, the problem of two-dimensional circular inhomogeneity (when the inserted material is of different size than the size of the cavity and having different elastic constants) is studiedin this paper. Stress could be bounded at infinity. The formulation is valid also for regions other then the circular ones when the matrix is finite has also been tackled. Numerical results are in conformity with the fact that the effect of couple stresses is negligible when the ratio of the smallest dimension of the body to the cahracteristic length is large.

Self-consistent theory of localization in weakly disordered systems

An analytic treatment of localization in a weakly disordered system is presented for the case where the real lattice is approximated by a Cayley tree. Contrary to a recent assertion we find that the mobility edge moves inwards into the band as disorder increases from zero.

A Comparative Study of Electrochemical Kinetic Parameters by the Potential Step Method. Electrode Reactions of CyDTA and EDTA Complexes of Cu(II) at DME

By using the same current-time (I-t) curves, electrochemical kinetic parameters are determined by two methods, (a) using the ratio of current at a given potential to the diffusion-controlled limiting current and (b) curve fitting method, for the reduction of Cu(II)–CyDTA complex. The analysis by the method (a) shows that the rate determining step involves only one electron although the overall reduction of the complex involves two electrons suggesting thereby the stepwise reduction of the complex. The nature of I-t curves suggests the adsorption of intermediate species at the electrode surface. Under these circumstances more reliable kinetic parameters can be obtained by the method (a) compared to that of (b). Similar observations are found in the case of reduction of Cu(II)–EDTA complex.

On the theory of polarographic maxima

The theory of polarographic maxima is presented taking into account the interaction of momentum transport, the electrostatic potential field, the adsorption—desorption and the faradaic processes. Several earlier results are generalised. The systems approach employed here is also extended to quasi-linear situations.

An electron spectroscopic study of the surface oxidation of glassy and crystalline Cu-Zr alloys

Surface oxidation of three metglasses in the Cu-Zr system has been investigated by employing X-ray photoelectron spectroscopy and Auger electron spectroscopy with a view to comparing their oxidation behaviour with that of the corresponding crystalline states of the alloys. Surface oxidation of pure Zr metal has also been examined in detail using these techniques. Sub-oxides of Zr are formed during the initial stages of oxidation of Zr (at oxygen exposures <10L), while at higher exposures, ZrO2 is formed together with the highest possible sub-oxide which the authors designate as 'ZrO'. The relative proportion of 'ZrO' goes through a maximum in the range 25-50 L. Both the glassy and the crystalline states of the Cu-Zr alloys exhibit preferential oxidation of Zr. The glassy alloys exhibit a higher rate of oxidation at intermediate exposures compared with the crystalline states of the alloys; the extent of oxidation at higher oxygen exposures is, however, higher for crystalline alloys. Interatomic Auger transitions have been found in the Zr+O2 system as well as in Cu-Zr alloys.

Optimal maintenance policy for equipment subject to random deterioration and random failure A modern control theory approach.

The stochastic version of Pontryagin's maximum principle is applied to determine an optimal maintenance policy of equipment subject to random deterioration. The deterioration of the equipment with age is modelled as a random process. Next the model is generalized to include random catastrophic failure of the equipment. The optimal maintenance policy is derived for two special probability distributions of time to failure of the equipment, namely, exponential and Weibull distributions Both the salvage value and deterioration rate of the equipment are treated as state variables and the maintenance as a control variable. The result is illustrated by an example

Orbit perturbation theory of beam-plasma instability

The nonlinear theory of the instability caused by an electron beam-plasma interaction is studied. A nonlinear analysis has been carried out using many-body methods. A general formula for a neutral collisionless plasma, without external fields, is derived. This could be used for calculating the saturation levels of other instabilities. The effect of orbit perturbation theory on the beam-plasma instability is briefly reviewed.

Application of molecular orbital theory to the interpretation of x-ray absorption spectra of platinum complexes

X-ray LIII-absorption edges of platinum in nine octahedral complexes have been recorded using a bent crystal spectrograph. The edge features of the discontinuities have been interpreted with the help of qualitative molecular orbital diagrams. A correlation between the energy separation of the first two absorption maxima and the spectrochemical series of the ligands has been arrived at.

Theory of CO2-laser induced x-ray emission from high density gaseous targets

Abstract is not available.

Theory of Non-linear Waves in Multi-dimensions: with Special Reference to Surface Water Waves

The surface water waves are "modal" waves in which the "physical space" (t, x, y, z) is the product of a propagation space (t, x, y) and a cross space, the z-axis in the vertical direction. We have derived a new set of equations for the long waves in shallow water in the propagation space. When the ratio of the amplitude of the disturbance to the depth of the water is small, these equations reduce to the equations derived by Whitham (1967) by the variational principle. Then we have derived a single equation in (t, x, y)-space which is a generalization of the fourth order Boussinesq equation for one-dimensional waves. In the neighbourhood of a wave froat, this equation reduces to the multidimensional generalization of the KdV equation derived by Shen & Keller (1973). We have also included a systematic discussion of the orders of the various non-dimensional parameters. This is followed by a presentation of a general theory of approximating a system of quasi-linear equations following one of the modes. When we apply this general method to the surface water wave equations in the propagation space, we get the Shen-Keller equation.