A Photoelectron Spectroscopic Study Of The Interaction Of Oxygen, Nitrogen And Transition-Metals With C-60 Films

Evidence is presented for the strong interaction of oxygen and nitrogen with solid films of buckminsterfullerene based on core-level spectroscopic studies. Cr, Ni and Cu deposited on C60 films interact strongly giving rise to large changes in the C(Is) and C(2p) binding energies as well as the (2p) binding energies of the transition metals.

Chemical potential of oxygen for iron-rutile-ilmenite and iron-ilmenite-ulvospinel equilibria

The chemical potential of oxygen corresponding to the iron-rutile-ilmenite (IRI) and iron-ilmenite-ulvospinel (IIU) equilibria has been measured employing solid-state galvanic cells,$$Pt, Fe + TiO_2 + FeTiO_3 //(Y_2 O_3 ) ZrO_2 //Fe + FeO, Pt$$ and $${\text{Pt, Fe + FeTiO}}_{\text{3}} {\text{ + Fe}}_{\text{2}} {\text{TiO}}_{\text{4}} {\text{//(Y}}_{\text{2}} {\text{0}}_{\text{3}} {\text{) ZrO}}_{\text{2}} {\text{//Fe + FeO, Pt}}$$ in the temperature range of 875 to 1275 K and 900 to 1373 K, respectively. The cells are written such that the right-hand electrodes are positive. The electromotive force (emf) of both the cells was found to be reversible and to vary linearly with temperature over the entire range of measurement. The chemical potential of oxygen for IRI equilibrium is represented by Δμo2(IRI) = -550,724 - 29.445T + 20.374T InT(±210) J mol−1 (875 <-T<- 1184 K) = -620,260 + 369.593T - 27.716T lnT(±210) J mol−1 (1184 <-T<- 1275 K) and that for IIU equilibrium by Δμo2(IIU) = -501,800 - 49.035T + 20.374T lnT(±210) J mol−1 (900 <-T<- 1184 K) = -571,336 + 350.003T− 27.716T lnT(=−210) J mol-1 (1184 <-T<- 1373 K) The standard Gibbs energy changes for IRI and IIU equilibria have been deduced from the measured oxygen potentials. Since ilmenite contains small amounts of Ti³+ ions, a correction for the activity of FeTiO3 has been incorporated by assuming ideal mixing on each cation sublattice in the FeTiO3-Ti2O3 system. Similarly, the ulvospinel contains some Fe³+ ions and a correction for the activity of Fe2TiO4 has been included by modeling the Fe2TiO4-Fe3O4 system. The third-law analysis of the results obtained for IRI equilibrium gives ΔH 298 0 = -575 (±1.0) kJ mol-1 and for IIU equilibrium yields ΔH 298 0 = -523.7 (±0.7) kJ mol−1}. The present results suggest that Fe2+ and Ti4+ cations mix almost ideally on the octahedral site of spinel lattice in Fe2TiO4, giving rise to a configurational contribution of 2R In 2 (11.5256 J mol-1 K-1) to the entropy of Fe2TiO4.

Effect of HCl on the adsorption of oxygen on Cu(110) surface: An eels study

Oxygen is shown to adsorb molecularly on a clean Cu(110) surface at 80 K and dissociate around 150 K forming atomic oxygen. Adsorption of oxygen on an HCl covered surface at low temperatures results in the formation of adsorbed hydroxyl groups and water in addition to adsorbed molecular oxygen. The molecular oxygen species is stable up to 190 K on the HCl covered surface.

Influence of various gases on single bubble sonoluminescence

Influence of various gases on the intensity of single bubble sonoluminescence has been studied. The gases used were air, oxygen, nitrogen, argon and helium. Among these oxygen gave the brightest intensity with nitrogen giving the least.

Nafion®-bound carbon electrodes containing transitionmetal phthalocyanines for oxygen reduction in solid-polymer-electrolyte fuel cells

Catalytic activities of some transition metal-phthalocyanine complexes towards electroreduction of molecular oxygen are examined on Nafion®-bound and bare porous carbon electrodes in 2.5 M H2SO4 electrolyte. It is found that these metal complexes exhibit better catalytic activities towards oxygen reduction with the Nafion®-bound electrodes.

Phase relations and thermodynamic properties of condensed phases in the system calcium-copper-oxygen

The isothermal sections of the phase diagram for the system Ca-Cu-0 at 1073 and 1223 K have been determined. Several compositions in the ternary system were quenched after equilibration, and the phases present were identified by optical microscopy, X-ray diffraction, and electron probe microanalysis. Two ternary compounds Ca2CuO3 and Cao.8&uO1.9s were identified at 1073 K. However, only Ca2CuO3 was found to be stable at 1223 K. The thermodynamic properties of the two ternary compounds were determined using solid-state cells incorporating either an oxide or a fluoride solid electrolyte. The results for both types of cells were internally consistent. The compound C ~ O . ~ & U Ow~h.i~ch~ c, a n also be represented as Ca15Cu18035h, as been identified in an earlier investigation as Cao.828CuOz. Using a novel variation of the galvanic cell technique, in which the emf of a cell incorporating a fluoride electrolyte is measured as a function of the oxygen potential of the gas phase in equilibrium with the condensed phase electrodes, it has been confirmed that the compound Cao.828CuO1.93 (Ca15Cu18035d) oes not have significant oxygen nonstoichiometry. Phase relations have been deduced from the thermodynamic data as a function of the partial pressure of oxygen for the system Ca-Cu-0 at 873, 1073, and 1223 K.

Relationship between the controllability grammian and closed-loop eigenvalues: the single input case

The controllability grammian is important in many control applications. Given a set of closed-loop eigenvalues the corresponding controllability grammian can be obtained by computing the controller which assigns the eigenvalues and then by solving the Lyapunov equation that defines the grammian. The relationship between the controllability grammian, resulting from state feedback, and the closed-loop eigenvalues of a single input linear time invariant (LTI) system is obtained. The proposed methodology does not require the computation of the controller that assigns the specified eigenvalues. The closed-loop system matrix is obtained from the knowledge of the open-loop system matrix, control influence matrix and the specified closed-loop eigenvalues. Knowing the closed-loop system matrix, the grammian is then obtained from the solution of the Lyapunov equation that defines it. Finally the proposed idea is extended to find the state covariance matrix for a specified set of closed-loop eigenvalues (without computing the controller), due to impulsive input in the disturbance channel and to solve the eigenvalue assignment problem for the single input case.

Matrix method for eigenvalue assignment: The single input case

The eigenvalue assignment/pole placement procedure has found application in a wide variety of control problems. The associated literature is rather extensive with a number of techniques discussed to that end. In this paper a method for assigning eigenvalues to a Linear Time Invariant (LTI) single input system is proposed. The algorithm determines a matrix, which has eigenvalues at the desired locations. It is obtained from the knowledge of the open-loop system and the desired eigenvalues. Solution of the matrix equation, involving unknown controller gains, open-loop system matrices and desired eigenvalues, results in the state feedback controller. The proposed algorithm requires the closed-loop eigenvalues to be different from those of the open-loop case. This apparent constraint is easily overcome by a negligible shift in the values. Two examples are considered to verify the proposed algorithm. The first one pertains to the in-plane libration of a Tethered Satellite System (TSS) while the second is concerned with control of the short period dynamics of a flexible airplane. Finally, the method is extended to determine the Controllability Grammian, corresponding to the specified closed-loop eigenvalues, without computing the controller gains.

Matrix method for eigenvalue assignment: The single input case

The eigenvalue assignment/pole placement procedure has found application in a wide variety of control problems. The associated literature is rather extensive with a number of techniques discussed to that end. In this paper a method for assigning eigenvalues to a Linear Time Invariant (LTI) single input system is proposed. The algorithm determines a matrix, which has eigenvalues at the desired locations. It is obtained from the knowledge of the open-loop system and the desired eigenvalues. Solution of the matrix equation, involving unknown controller gains, open-loop system matrices and desired eigenvalues, results in the state feedback controller. The proposed algorithm requires the closed-loop eigenvalues to be different from those of the open-loop case. This apparent constraint is easily overcome by a negligible shift in the values. Two examples are considered to verify the proposed algorithm. The first one pertains to the in-plane libration of a Tethered Satellite System (TSS) while the second is concerned with control of the short period dynamics of a flexible airplane. Finally, the method is extended to determine the Controllability Grammian, corresponding to the specified closed-loop eigenvalues, without computing the controller gains.

Origin of the insulating state in NaCuO2

We study the electronic structure of NaCuO2 by analysing experimental core level photoemission and X-ray absorption spectra using a cluster as well as an Anderson impurity Hamiltonian including the band structure of the oxygen sublattice. We show that the X-ray absorption results unambiguously establish a negative value of the charge transfer energy, A. Further, mean-field calculations for the edge-shared one-dimensional CuO2 lattice of NaCuO2 within the multiband Hubbard Hamiltonian show that the origin of the insulating nature lies in the band structure rather than in the correlation effects. LMTO-ASA band structure calculations suggest that NaCuO2 is an insulator with a gap of around 1 eV.

Study of the reaction between 1,2,3-trihydroxybenzene and 8-hydroxyquinoline in the solid state

1.2,3-Trihydroxybenzene (THB) reacts with 8-hydroxyquinoline (8HQ) in the solid state forming an orange-coloured charge transfer complex THB* (8HQ)(2). When the reaction was carried out in a petri dish, or when the vapours of 8HQ were allowed to react with solid THB (gravimetric study), the reaction product separated out as good quality, shiny single crystals. X-Ray diffraction studies on single crystals showed that they belong to the orthorhombic system with a = 15.408(1), b = 16.276(1), c = 7.825(1) Angstrom, Z = 4, D-x = 1.413 g cm(-3) and space group Pnaa. From the crystallographic evidence it has been found that the proton of the middle OH group of THB is transferred to the N atom of 8HQ. This accounts for the observed colour change. Kinetic studies on the solid state reaction showed that the 8HQ molecules diffuse towards THB, and the lateral diffusion occurs through surface migration, grain boundary diffusion and vapour phase diffusion. Gravimetric studies of the reaction between solid THB and 8HQ vapour showed that the diffusion of 8HQ molecules into the crystal lattice of THB has a higher energy of activation than that observed when the reactants are in contact. The nature of the crystal packing in the reaction product indicates diffusion of 8HQ molecules into the crystal lattice of THB along the c-axis, to occupy the cavities present between the THB molecules in the unit cell.

A single network adaptive critic (SNAC) architecture for optimal control synthesis for a class of nonlinear systems

Even though dynamic programming offers an optimal control solution in a state feedback form, the method is overwhelmed by computational and storage requirements. Approximate dynamic programming implemented with an Adaptive Critic (AC) neural network structure has evolved as a powerful alternative technique that obviates the need for excessive computations and storage requirements in solving optimal control problems. In this paper, an improvement to the AC architecture, called the �Single Network Adaptive Critic (SNAC)� is presented. This approach is applicable to a wide class of nonlinear systems where the optimal control (stationary) equation can be explicitly expressed in terms of the state and costate variables. The selection of this terminology is guided by the fact that it eliminates the use of one neural network (namely the action network) that is part of a typical dual network AC setup. As a consequence, the SNAC architecture offers three potential advantages: a simpler architecture, lesser computational load and elimination of the approximation error associated with the eliminated network. In order to demonstrate these benefits and the control synthesis technique using SNAC, two problems have been solved with the AC and SNAC approaches and their computational performances are compared. One of these problems is a real-life Micro-Electro-Mechanical-system (MEMS) problem, which demonstrates that the SNAC technique is applicable to complex engineering systems.

Interaction of nitrogen and oxygen with C60

Evidence is presented for the strong interaction of nitrogen and oxygen with buckminsterfullerene.

Effect of thermal annealing on the dielectric properties of KTiOPO4 single crystals

Dielectric properties of potassium titanyl phosphate have been investigated as a function of thickness and frequency, as well as annealing treatment under various atmospheres. The low frequency dielectric constant of KTP crystals is shown to depend upon the sample thickness, and this feature is attributed to the existence of surface layers. The frequency-dependent dielectric response of KTP exhibits a non-Debye type relaxation, with a distribution of relaxation times. The dielectric behavior of KTP samples annealed in various atmospheres shows that the low frequency dielectric constant is influenced by the contribution from the space charge layers. Prolonged annealing of the samples leads to a surface degradation, resulting in the formation of a surface layer of lower dielectric constant. This surface degradation is least when annealed in the presence of dry oxygen. From the analysis of the dielectric data using complex electric modulus, alpha(m) has been evaluated for the virgin and annealed samples. (C) 1996 American Institute of Physics.

Interaction of single-walled carbon nanotubes with poly(propyl ether imine) dendrimers

We study the complexation of nontoxic, native poly(propyl ether imine) dendrimers with single-walled carbon nanotubes (SWNTs). The interaction was monitored by measuring the quenching of inherent fluorescence of the dendrimer. The dendrimer-nanotube binding also resulted in the increased electrical resistance of the hole doped SWNT, due to charge-transfer interaction between dendrimer and nanotube. This charge-transfer interaction was further corroborated by observing a shift in frequency of the tangential Raman modes of SWNT. We also report the effect of acidic and neutral pH conditions on the binding affinities. Experimental studies were supplemented by all atom molecular dynamics simulations to provide a microscopic picture of the dendrimer-nanotube complex. The complexation was achieved through charge transfer and hydrophobic interactions, aided by multitude of oxygen, nitrogen, and n-propyl moieties of the dendrimer. (C) 2011 American Institute of Physics. doi:10.1063/1.3561308]