Monte Carlo and molecular dynamics simulation of argon clusters andn-alkanes in the confined regions of zeolites

Geometry and energy of argon clusters confined in zeolite NaCaA are compared with those of free clusters. Results indicate the possible existence of magic numbers among the confined clusters. Spectra obtained from instantaneous normal mode analysis of free and confined clusters give a larger percentage of imaginary frequencies for the latter indicating that the confined cluster atoms populate the saddle points of the potential energy surface significantly. The variation of the percentage of imaginary frequencies with temperature during melting is akin to the variation of other properties. It is shown that confined clusters might exhibit inverse surface melting, unlike medium-to-large-sized free clusters that exhibit surface melting. Configurational-bias Monte Carte (CBMC) simulations of n-alkanes in zeolites Y and A are reported. CBMC method gives reliable estimates of the properties relating to the conformation of molecules. Changes in the conformational properties of n-butane and other longer n-alkanes such as n-hexane and n-heptane when they are confined in different zeolites are presented. The changes in the conformational properties of n-butane and n-hexane with temperature and concentration is discussed. In general, in zeolite Y as well as A, there is significant enhancement of the gauche population as compared to the pure unconfined fluid.

Structural evolution and electronic properties of La1+xSr2-xMn2O7

A detailed study of the layered manganite La1+xSr2-xMn2O7 has been performed, establishing that within the composition range 0.1 less than or equal to x less than or equal to 0.45 the phases crystallize in the I4/mmm space group. The evolution of structural parameters with x: in this composition range has been followed using a novel application of an existing program for the Rietveld analysis of powder diffraction data. The structure, a familiar intergrowth of rock-salt (La,Sr)O slabs and double perovskite (La,Sr)(2)Mn2O6 units, is characterized by a reluctance to deform the latter. This manifests as a ''pumping'' of the larger Sr-II ion into the 12-coordinate site of the structure as x is increased. We report these features of the structure as well as electrical transport and magnetic properties, in light of recent observations of giant, negative magnetoresistance in these systems.

Modulation of lifetimes and diastereomeric discrimination in triplet-excited substituted butane-1,4-diones through intramolecular charge-transfer quenching

Triplet lifetimes have been determined for the diastereomers of a broad set of butane-l,4-dione derivatives (1-3). A remarkable dependence of lifetimes on conformational preferences is revealed in that the lifetimes are shorter for the meso diastereomers of 1-3 than those for the racemic ones. The intramolecular beta-phenyl quenching is promoted in the case of meso diastereomers by virtue of the gauche relationship between the excited carbonyl group and the beta-aryl ring, while a distal arrangement in the lowest energy conformation (H-anti) in racemic diastereomers prevents such a deactivation. The involvement of charge transfer in the intramolecular beta-phenyl quenching is suggested by the correlation of the triplet lifetimes of the meso diastereomers of compounds 2 with the nature of the substituent on the beta-phenyl rings. In the case of racemic diastereomers, beta-methoxy substitution on the beta-phenyl ring (2-OCH3, 3-OCH3) also led to a decrease of the triplet lifetimes when compared to those of the nonsubstituted compounds (2-H, 3-H). This shortening is accounted for by the deactivation of a small proportion of the excited molecules through beta-phenyl quenching. In addition to the above factors, the lifetimes in the case of meso diastereomers can further be controlled by increasing the energy spacing between the T-1 and T-2 states, since beta-phenyl quenching occurs from the latter for compounds 2 and 3. Through a rational conformational control, a surprisingly long triplet lifetime (300 ns) has been measured for the first time for a purely n,pi* triplet-excited beta-phenylpropiophenone dimer (1-rac).

Jointly Optimal MMSE design for non-redundant FIR precoding and equalization

We provide a filterbank precoding framework (FBP) for frequency selective channels using the minimum mean squared error (MMSE) criterion. The design obviates the need for introducing a guard interval between successive blocks, and hence can achieve the maximum possible bandwidth efficiency. This is especially useful in cases where the channel is of a high order. We treat both the presence and the absence of channel knowledge at the transmitter. In the former case, we obtain the jointly optimal precoder-equalizer pair of the specified order. In the latter case, we use a zero padding precoder, and obtain the MMSE equalizer. No restriction on the dimension or nature of the channel matrix is imposed. Simulation results indicate that the filterbank approach outperforms block based methods like OFDM and eigenmode precoding.

A Raman study of CdSe and ZnSe nanostructures

Raman studies have been carried out on CdSe nanotubes and ZnSe nanorods produced by surfactant-assisted synthesis. The Raman spectrum of CdSe nanotubes shows modes at 207.5 and 198 cm(-1); the former arises from the longitudinal optic phonon mode red-shifted with respect to the bulk mode because of phonon confinement, and the latter is the I = 1 surface phonon. Analysis based on the phonon confinement model demonstrates that the size of the nanoparticle responsible for the red-shift is about 4 nm, close to the estimate from the blue-shift of the photoluminescence. The Raman spectrum of ZnSe,nanorods shows modes at 257 and 213 cm(-1), assigned to longitudinal and transverse optic phonons, blue-shifted with respect to the bulk ZnSe modes because of compressive strain. The mode at 237 cm(-1) is the surface phonon.

Driven Heisenberg magnets: Nonequilibrium criticality, spatiotemporal chaos and control

We drive a d-dimensional Heisenberg magnet using an anisotropic current. The continuum Langevin equation is analysed using a dynamical renormalization group and numerical simulations. We discover a rich steady-state phase diagram, including a critical point in a new nonequilibrium universality class, and a spatiotemporally chaotic phase. The latter may be controlled in a robust manner to target spatially periodic steady states with helical order.

Modeling re-ignition and chuffing in solid rocket motors

A nonlinear model is developed to numerically simulate dynamic combustion inside a solid rocket motor chamber. Using this model, the phenomena of re-ignition and chuffing are investigated under low-L* conditions. The model consists of two separate submodels (coupled to each other), one for unsteady burning of propellant and the other for unsteady conservation of mass and energy within the chamber. The latter yields instantaneous pressure and temperature within the chamber. The instantaneous burning rate is calculated using a one-dimensional, nonlinear, transient gas-phase model previously developed by the authors. The results presented in this paper show that the model predicts not only the critical L*, but also the various regimes of L*-instabihty. Specifically, the results exhibit (1) amplifying pressure oscillations leading to extinction, and (2) re-ignition after a dormant period following extinction. The re-ignition could be observed only when a radiation heat flux (from the combustion chamber to the propellant surface) was included. Certain high-frequency oscillations, possibly due to intrinsic instability, are observed when the pressure overshoots during re-ignition. At very low values of initial L*, successive cycles of extinction/reignition displaying typical characteristics of chuffing are predicted. Variations of the chuffing frequency and the thickness of propellant burned off during a chuff with L* are found to be qualitatively the same as that reported from experimental observations.

Solvothermal routes to capped oxide and chalcogenide nanoparticles

We review our recent contributions to the use of solvothermal methods for the preparation of different oxide and chalcogenide nanoparticles. We have prepared sub 10-nm,gamma-Fe2O3 ZnFe2O4, and CoFe2O4 particles by the decomposition of the corresponding cupferron complexes in the presence of n-octylamine or n-dodecylamine in solvothermal toluene. Similarly, dodecanethiol-capped chalcogenide nanoparticles of CdSe have been prepared by reacting cadmium stearates with H2Se under solvothermal conditions. The H2Se is generated in situ by the reduction of Se by tetralin. Using this latter technique, we have also been able to prepare PbSe and PbI2 in toluene under solvothermal conditions, albeit in bulk (rather than nanocrystalline) form. In the preparation of PbI2, HI is prepared by the in situ reduction of I-2 by tetralin.

Synthesis of acicular hydrogoethite (alpha-FeOOH center dot xH(2)O; 0.1 < x < 0.22) particles using morphology controlling cationic additives and magnetic properties of maghemite derived from hydrogoethite

A method for the preparation of acicular hydrogoethite (alpha -FeOOH.xH(2)O, 0.1 < x < 0.22) particles of 0.3-1 mm length has been optimized by air oxidation of Fe( II) hydroxide gel precipitated from aqueous (NH4)(2)Fe(SO4)(2) solutions containing 0.005-0.02 atom% of cationic Pt, Pd or Rh additives as morphology controlling agents. Hydrogoethite particles are evolved from the amorphous ferrous hydroxide gel by heterogeneous nucleation and growth. Preferential adsorption of additives on certain crystallographic planes thereby retarding the growth in the perpendicular direction, allows the particles to acquire acicular shapes with high aspect ratios of 8-15. Synthetic hydrogoethite showed a mass loss of about 14% at similar to 280 degreesC, revealing the presence of strongly coordinated water of hydration in the interior of the goethite crystallites. As evident from IR spectra, excess H2O molecules (0.1- 0.22 per formula unit) are located in the strands of channels formed in between the double ribbons of FeO6 octahedra running parallel to the c- axis. Hydrogoethite particles constituted of multicrystallites are formed with Pt as additive, whereas single crystallite particles are obtained with Pd (or Rh). For both dehydroxylation as well as H-2 reduction, a lower reaction temperature (similar to 220 degreesC) was observed for the former (Pt treated) compared to the latter (Pd or Rh) (similar to 260 degreesC). Acicular magnetite (Fe3O4) was prepared either by reducing hydrogoethite (magnetite route) or dehydroxylating hydrogoethite to hematite and then reducing it to magnetite (hematite- magnetite route). According to TEM studies, preferential dehydroxylation of hydrogoethite along < 010 > leads to microporous hematite. Maghemite (gamma -Fe2O3 (-) (delta), 0 < < 0.25) was obtained by reoxidation of magnetite. The micropores are retained during the topotactic transformation to magnetite and finally to maghemite, whereas cylindrical mesopores are formed due to rearrangement of the oxygen sublattice from hexagonal to cubic close packing during the conversion of hydrogoethite to magnetite and then to maghemite. Accordingly, three different types of maghemite particles are realized: strongly oriented multicrystalline particles, single crystalline acicular particles with micropores or crystallites having mesopores. Higher values of saturation magnetization ((s) = 74 emu g(-1)) and coercivity (H-c = 320 Oe) are obtained for single crystalline mesoporous particles. In the other cases, the smaller size of particles and larger distribution of micropores decreases sigma (s) considerably ( < 60 emu g(-1)) due to relaxation effects of spins on the surface atoms as revealed by Mossbauer spectroscopy.

Carbothermal reduction and nitridation reaction of SiOx and preoxidized SiOx: Formation of α-Si3N4 fibers

The chemical composition of amorphous SiOx has been analyzed by oxidation studies and is found to be SiO1.7. SiO1.7 appears to be a monophasic amorphous material on the basis of 29Si nuclear magnetic resonance, high resolution electron microscopy, and comparative behavior of a physical mixture of Si and SiO2. Carbothermal reduction and nitridation reactions have been carried out on amorphous SiO1.7 and on amorphous SiO2 obtained from oxidation of SiO1.7. At 1623 K reactions of SiO1.7 lead exclusively to the formation of Si2N2O, while those of SiO2 lead exclusively to the formation of Si3N4. Formation of copious fibers of α-Si3N4 was observed in the latter reaction. It is suggested that the partial pressure of SiO in equilibrium with reduced SiO1.7 and SiO2 during the reaction is the crucial factor that determines the chemistry of the products. The differences in the structures of SiO2 and SiO1.7 have been considered to be the origin of the differences in the SiO partial pressures of the reduction products formed prior to nitridation. The effect of the ratios, C:SiO1.7 and C:SiO2, in the reaction mixture as well as the effect of the temperature on the course of the reactions have also been investigated.

Microwave ECR Plasma Assisted MOCVD of Y(2)O(3) Thin Films Using Y(tod)(3) Precursor and Their Characterization

Yttrium oxide (Y(2)O(3)) thin films were deposited by microwave electron cyclotron resonance (ECR) plasma assisted metal organic chemical vapour deposition (MOCVD) process using indigenously developed metal organic precursors Yttrium 2,7,7-trimethyl-3,5-octanedionates, commonly known as Y(tod)(3) which were synthesized by an ultrasound method. A series of thin films were deposited by varying the oxygen flow rate from 1-9 sccm, keeping all other parameters constant. The deposited coatings were characterized by X-ray photoelectron spectroscopy, glancing angle X-ray diffraction and infrared spectroscopy. Thickness and roughness for the films were measured by stylus profilometry. Optical properties of the coatings were studied by the spectroscopic ellipsometry. Hardness and elastic modulus of the films were measured by nanoindentation technique. Being that microwave ECR CVD process is operating-pressure-sensitive, optimum oxygen activity is very essential for a fixed flow rate of precursor, in order to get a single phase cubic yttrium oxide in the films. To the best of our knowledge, this is the first effort that describes the use of Y(tod)(3) precursor for deposition of Y(2)O(3) films using plasma assisted CVD process.

Conformational studies of the phosphazenyl side chain in cyclophosphazenes. Part 3. Crystal and molecular structure of N3P3Cl4(NEt2)(NPPh3)

The crystal structure of N3P3Cl4(NEt2)(NPPh3) has been determined. The crystals are orthorhombic, space group Pbca, with a= 8.208(1), b= 21.890(1), c= 31.722(2)Å, Z= 8, and m.p. = 146.5 °C. The structure was solved by direct methods and refined to a final R value of 0.045 for 2 025 independent reflections. The analysis reveals significant variations in the ring P–N bond lengths. The two nitrogenous substituents, NPPh3 and NEt2, reside on the same phosphorus atom. The latter, NEt2, has an almost exact type II conformation (the plane NC2 almost perpendicular to the local NPN plane)(the first observed for a dialkylamino-group in cyclophosphazenes), the former, NPPh3, deviates from type II towards type III (in type III the plane Pring–N–Pexo makes an angle of ca. 45° with the local N–P–N ring plane). The present structure is compared with others of triphenylphosphazenyl-cyclophosphazenes and the conformation of the NPPh3 substituent and its electron supply in the ground and perturbed states are discussed.

Laboratory simulations show diabatic heating drives cumulus-cloud evolution and entrainment

Clouds are the largest source of uncertainty in climate science, and remain a weak link in modeling tropical circulation. A major challenge is to establish connections between particulate microphysics and macroscale turbulent dynamics in cumulus clouds. Here we address the issue from the latter standpoint. First we show how to create bench-scale flows that reproduce a variety of cumulus-cloud forms (including two genera and three species), and track complete cloud life cycles-e.g., from a ``cauliflower'' congestus to a dissipating fractus. The flow model used is a transient plume with volumetric diabatic heating scaled dynamically to simulate latent-heat release from phase changes in clouds. Laser-based diagnostics of steady plumes reveal Riehl-Malkus type protected cores. They also show that, unlike the constancy implied by early self-similar plume models, the diabatic heating raises the Taylor entrainment coefficient just above cloud base, depressing it at higher levels. This behavior is consistent with cloud-dilution rates found in recent numerical simulations of steady deep convection, and with aircraft-based observations of homogeneous mixing in clouds. In-cloud diabatic heating thus emerges as the key driver in cloud development, and could well provide a major link between microphysics and cloud- scale dynamics.

Thermodynamic properties of Ln-O (Ln = La, Pr, Nd) solid solutions and their deoxidation by molten salt electrolysis

The lanthanide metals lanthanum, praseodymium and neodymium containing 2,200, 2,600, 1,850 mass ppm oxygen, respectively, were deoxidized to 20-30 ppm level at 1,073 K by an electrochemical method. The metal to be deoxidized was used as the cathode in an electrolysis cell which consisted of a graphite anode and molten CaCl2 electrolyte. The calcium metal produced at the cathode by electrolysis effectively deoxidized the lanthanide metal. Calcium oxide produced by deoxidation, dissolved in the melt. The liberation of carbon monoxide/dioxide at the anode was found to prevent accumulation of oxygen in the melt. For a quantitative discussion of the limits of deoxidation achievable by this technique, a thermodynamic investigation of the lanthanide-oxygen (Ln-O ; Ln = La, Pr, Nd) solid solutions was conducted. The lanthanide metal, yttrium and titanium samples were immersed in calcium-saturated CaCl2 melt, containing a small quantity of dissolved CaO, at 1,093 K. The oxygen potential of the melt and the Ln-O solid solutions were obtained from the oxygen content of yttrium samples at equilibrium, and the known thermodynamic properties of yttrium-oxygen solid solution. The results were confirmed by using Y/Y2O3 equilibrium to control the oxygen potential of the molten salt reservoir. The oxygen affinity of the metals was found to decrease in the order : Y > Ti > Nd > Pr > La. The deoxidation results are consistent with the thermodynamic properties of the RE-O solid solutions.

Improving Superscalar Instruction Dispatch And Issue By Exploiting Dynamic Code Sequences

Superscalar processors currently have the potential to fetch multiple basic blocks per cycle by employing one of several recently proposed instruction fetch mechanisms. However, this increased fetch bandwidth cannot be exploited unless pipeline stages further downstream correspondingly improve. In particular,register renaming a large number of instructions per cycle is diDcult. A large instruction window, needed to receive multiple basic blocks per cycle, will slow down dependence resolution and instruction issue. This paper addresses these and related issues by proposing (i) partitioning of the instruction window into multiple blocks, each holding a dynamic code sequence; (ii) logical partitioning of the registerjle into a global file and several local jles, the latter holding registers local to a dynamic code sequence; (iii) the dynamic recording and reuse of register renaming information for registers local to a dynamic code sequence. Performance studies show these mechanisms improve performance over traditional superscalar processors by factors ranging from 1.5 to a little over 3 for the SPEC Integer programs. Next, it is observed that several of the loops in the benchmarks display vector-like behavior during execution, even if the static loop bodies are likely complex for compile-time vectorization. A dynamic loop vectorization mechanism that builds on top of the above mechanisms is briefly outlined. The mechanism vectorizes up to 60% of the dynamic instructions for some programs, albeit the average number of iterations per loop is quite small.