Investigations of superconducting bismuth cuprates of the general formula Bi2-xPbx(Ca,Sr,Y)n 1 Cun O2n 4 δ

In the (Bi,Pb)-Sr-Cu-O system we have examined many compositions which are either metallic or semiconducting. In the Bi2-xPbx(Ca, Sr)n+1 Cun O2n+4+δ system, we have established the superconducting properties of the n = 1 to 4 members. The Tc increases from n = 1 to 3 and does not increase further when n = 4. In Bi2Ca1-x,YxSr2Cu2Oy, the Tc decreases with increase in x.

Electronic structures of electron donor-acceptor complexes: results from ultraviolet photoelectron spectroscopy and molecular orbital calculations

HeI photoelectron spectra of 1:1 electron donor-acceptor complexes are discussed in the light of molecular orbital calculations. The complexes discussed include those formed by BH3, BF3 and SO2. Some systematics have been found in the ionization energy shifts of the complexes compared to the free components and these are related to the strength of the donor-acceptor bond. Hel spectra of hydrogen bonded complexes are discussed in comparison with results from MO calculations. Limitations of such studies as well as scope for further investigations are indicated.

Photodissociation of isomeric dichloroethylenes in the ultraviolet: Effect of the second chlorine atom substitution on the dynamics

We report the Cl-*(P-2(1/2)) production dynamics in the near-UV dissociation of three isomers (cis-, gem-, and trans-) of dichloroethylene using the conventional resonance enhanced multiphoton ionization technique. Substantial amounts of Cl-* are produced in the wavelength range 222-304 nm. The Cl-* quantum yield (phi(*)) i maximum at 304 nm for all the isomers and phi(*)(cis) is markedly higher than phi(*)(gem) and phi(*)(trans) except at 222 nm. Existence of both direct and indirect dissociation pathways at these wavelengths complicates the Cl* production dynamics. The higher value of phi(*)(cis) originates from a large contribution from direct dissociation via the (n, sigma(*)) state.

The Shannon Cipher System with a Guessing Wiretapper: General Sources

The Shannon cipher system is studied in the context of general sources using a notion of computational secrecy introduced by Merhav & Arikan. Bounds are derived on limiting exponents of guessing moments for general sources. The bounds are shown to be tight for iid, Markov, and unifilar sources, thus recovering some known results. A close relationship between error exponents and correct decoding exponents formfixed rate source compression on the one hand and exponents for guessing moments on the other hand is established.

A general thermodynamic framework for understanding the behaviour of absorption chillers

In this article, a general definition of the process average temperature has been developed, and the impact of the various dissipative mechanisms on 1/COP of the chiller evaluated. The present component-by-component black box analysis removes the assumptions regarding the generator outlet temperature(s) and the component effective thermal conductances. Mass transfer resistance is also incorporated into the absorber analysis to arrive at a more realistic upper limit to the cooling capacity. Finally, the theoretical foundation for the absorption chiller T-s diagram is derived. This diagrammatic approach only requires the inlet and outlet conditions of the chiller components and can be employed as a practical tool for system analysis and comparison. (C) 2000 Elsevier Science Ltd and IIR. All rights reserved.

Steric effects on the ultraviolet absorption of 1,2-enedioic and related systems

1,2-Enedioic systems, being sterically perturbed from planarity do not show the effect of the extended conjugation expected of a (formal) trienic entity. In the absence of a model which approximates to a uniplanar situation, the strategy of replacing an ester group in the enedioates by a cyano (for which less stringent steric demand may be presumed) and noting the correction concomitant to this replacement was adopted to arrive at a notional figure for the position of maximal absorption in the planar enedioates. From this the conclusion, subject to substantiation by molecular mechanical or quantum chemical calculations, was drawn that even the E-isomeric and comparatively less substituted enedioates are highly sterically perturbed. An alternative to an earlier explanation of the bathochromic shift of absorption maxima encountered in the 5-cyclic ene-ester and ene-nitrile, relative to the 6-cyclic analogues (observed also with the enedioates and cyanovinyl ester systems), seen later to have been based on unwarranted premises, has been advanced. A comment on the absorption characteristics of enedioic anhydrides has been appended.

An ultraviolet photoelectron spectroscopic study of BF3–donor complexes

He i spectra of strong n–v type adducts of BF3 with H2O, CH3OH, (C2H5)2O, and CH3CN as well as of weak complexes of BF3 with NO and H2S are reported along with assignments based on MO calculations. The energy of the fluorine orbitals of BF3 is shown to be shifted in proportion to the strength of the donor–acceptor interaction. BF3 seems to form a contact pair with CS2.

A general procedure for generation of curved DNA molecules.

A general method for generation of base-pairs in a curved DNA structure, for any prescribed values of helical parameters--unit rise (h), unit twist (theta), wedge roll (theta R) and wedge tilt (theta T), propeller twist (theta p) and displacement (D) is described. Its application for generation of uniform as well curved structures is also illustrated with some representative examples. An interesting relationship is observed between helical twist (theta), base-pair parameters theta x, theta y and the wedge parameters theta R, theta T, which has important consequences for the description and estimation of DNA curvature.

Distributed nonlinear optimization algorithms for general network problems

There are a number of large networks which occur in many problems dealing with the flow of power, communication signals, water, gas, transportable goods, etc. Both design and planning of these networks involve optimization problems. The first part of this paper introduces the common characteristics of a nonlinear network (the network may be linear, the objective function may be non linear, or both may be nonlinear). The second part develops a mathematical model trying to put together some important constraints based on the abstraction for a general network. The third part deals with solution procedures; it converts the network to a matrix based system of equations, gives the characteristics of the matrix and suggests two solution procedures, one of them being a new one. The fourth part handles spatially distributed networks and evolves a number of decomposition techniques so that we can solve the problem with the help of a distributed computer system. Algorithms for parallel processors and spatially distributed systems have been described.There are a number of common features that pertain to networks. A network consists of a set of nodes and arcs. In addition at every node, there is a possibility of an input (like power, water, message, goods etc) or an output or none. Normally, the network equations describe the flows amoungst nodes through the arcs. These network equations couple variables associated with nodes. Invariably, variables pertaining to arcs are constants; the result required will be flows through the arcs. To solve the normal base problem, we are given input flows at nodes, output flows at nodes and certain physical constraints on other variables at nodes and we should find out the flows through the network (variables at nodes will be referred to as across variables).The optimization problem involves in selecting inputs at nodes so as to optimise an objective function; the objective may be a cost function based on the inputs to be minimised or a loss function or an efficiency function. The above mathematical model can be solved using Lagrange Multiplier technique since the equalities are strong compared to inequalities. The Lagrange multiplier technique divides the solution procedure into two stages per iteration. Stage one calculates the problem variables % and stage two the multipliers lambda. It is shown that the Jacobian matrix used in stage one (for solving a nonlinear system of necessary conditions) occurs in the stage two also.A second solution procedure has also been imbedded into the first one. This is called total residue approach. It changes the equality constraints so that we can get faster convergence of the iterations.Both solution procedures are found to coverge in 3 to 7 iterations for a sample network.The availability of distributed computer systems — both LAN and WAN — suggest the need for algorithms to solve the optimization problems. Two types of algorithms have been proposed — one based on the physics of the network and the other on the property of the Jacobian matrix. Three algorithms have been deviced, one of them for the local area case. These algorithms are called as regional distributed algorithm, hierarchical regional distributed algorithm (both using the physics properties of the network), and locally distributed algorithm (a multiprocessor based approach with a local area network configuration). The approach used was to define an algorithm that is faster and uses minimum communications. These algorithms are found to converge at the same rate as the non distributed (unitary) case.

Evidence for double valence fluctuation in metallic oxides of lead

The possible role of double valence fluctuation in both lead and oxide ions with reference to metallization in oxides of lead is examined by x-ray-photoemission spectroscopy, ultraviolet-photoemission spectroscopy (UPS), and 207Pb NMR studies. The double valence fluctuations may be viewed as Pb4++2O2-⇄Pb2+O22-. While the insulating oxides PbO, Pb3O4, and Sr2PbO4 show a single oxide ion, O2- characterized by O(1s) at 529.7 eV, the insulating peroxide BaO2 is characterized by the ion O22- with a single O(1s) at 533 eV. The metallic PbO2, BaPbO3, BaBiPbO3, and SrPbO3 showed the occurrence of both O2- and O22- ions. The valence band in these compounds has also been studied by UPS, and clear evidence for the coexistence of O2- and O22- is seen in PbO2. A simultaneous study of 207Pb NMR suggests that the Pb ion could also exist in mixed-valence states. Qualitative arguments are presented to rationalize the existence of such mixed valences of the anion in metal oxides in general and their role in superconductivity.

Optimal infinite-horizon feedback laws for a general class of constrained discrete-time systems: stability and moving-horizon approximations

Stability results are given for a class of feedback systems arising from the regulation of time-varying discrete-time systems using optimal infinite-horizon and moving-horizon feedback laws. The class is characterized by joint constraints on the state and the control, a general nonlinear cost function and nonlinear equations of motion possessing two special properties. It is shown that weak conditions on the cost function and the constraints are sufficient to guarantee uniform asymptotic stability of both the optimal infinite-horizon and movinghorizon feedback systems. The infinite-horizon cost associated with the moving-horizon feedback law approaches the optimal infinite-horizon cost as the moving horizon is extended.

Design and fabrication of an indigenous molecular beam ultraviolet photoelectron spectrometer

An ultraviolet photoelectron spectrometer for the study of van der Waals molecules has been designed and fabricated indigenously. The spectrometer consists of an HeI discharge lamp, a molecular beam sample inlet system, an electrostatic lens, a 180-degrees hemispherical electrostatic analyser and a channeltron detector. Performance of the spectrometer is illustrated with an example.

Vacuum ultraviolet circular dichroism spectrum of β-turn in solution

The vacuum ultraviolet circular dichroism spectrum of an isolated 4 → 1 hydrogen bonded β-turn is reported. The observed spectrum of N-acetyl-Pro-Gly-Leu-OH at − 40°C in trifluoroethanol is in good agreement with the theoretically calculated CD spectrum of the β-turn conformation. This spectrum, particularly the presence of a strong negative band around 180 nm and a large ratio [θ]201/[θ]225, can be taken as a characteristic feature of the isolated β-turn conformation. These CD spectral features can thus be used to distinguish the β-turn conformation from the β-structure in solution.

Transition metal oxide perovskites by photoelectron and x-ray absorption spectroscopy

X-ray and ultraviolet photoelectron spectroscopy as well as x-ray absorption spectroscopy have been employed to investigate transition metal oxide perovskites of the general formula ABOs (A=La or rare-earth ion, B=trivalent transition metalion). Systematics in the core levels and in the valence bands in the series of LaBOa compounds have been discussed. Lanthanum chemical shifts in the x-ray absorption spectra in this series show interesting trends. Photoelectron spectra of the solid solutions, LaNil_x Coxes, LaNix_x FexO8 and LaFel_x Coxes show that the rigid band model is applicable to these systems. It is shown that x-ray photoelectron spectroscopy can be employed to identify multiple oxidation states of transition metal ions in oxide perovskites.