Infrared Spectra of Dimethylquinolines in the Gas Phase: Experiment and Theory

Infrared spectra of atmospherically important dimethylquinolines (DMQs), namely 2,4-DMQ, 2,6-DMQ, 2,7-DMQ, and 2,8-DMQ in the gas phase at 80 degrees C were recorded using a long variable path-length cell. DFT calculations were carried out to assign the bands in the experimentally observed spectra at the B3LYP/6-31G* level of theory. The spectral assignments particularly for the C-H stretching modes could not be made unambiguously using calculated anharmonic or scaled harmonic frequencies. To resolve this problem, a scaled force field method of assignment was used. Assignment of fundamental modes was confirmed by potential energy distributions (PEDs) of the normal modes derived by the scaled force fields using a modified version of the UMAT program in the QCPE package. We demonstrate that for large molecules such as the DMQs, the scaling of the force field is more effective in arriving at the correct assignment of the fundamentals for a quantitative vibrational analysis. An error analysis of the mean deviation of the calculated harmonic, anharmonic, and force field fitted frequencies from the observed frequency provides strong evidence for the correctness of the assignment.

Identification of corona discharge-induced SF6 oxidation mechanisms using SF6/18O2/H216O and SF6/16O2/H218O gas mixtures

The absolute yields of gaseous oxyfluorides SOF2, SO2F2, and SOF4 from negative, point-plane corona discharges in pressurized gas mixtures of SF6 with O2 and H2O enriched with18O2 and H2 18O have been measured using a gas chromatograph-mass spectrometer. The predominant SF6 oxidation mechanisms have been revealed from a determination of the relative18O and16O isotope content of the observed oxyfluoride by-product. The results are consistent with previously proposed production mechanisms and indicate that SOF2 and SO2F2 derive oxygen predominantly from H2O and O2, respectively, in slow, gas-phase reactions involving SF4, SF3, and SF2 that occur outside of the discharge region. The species SOF4 derives oxygen from both H2O and O2 through fast reactions in the active discharge region involving free radicals or ions such as OH and O, with SF5 and SF4.

Modified governing equations for gas-particle nozzle flows

A modified set of governing equations for gas-particle flows in nozzles is suggested to include the inertial forces acting on the particle phase. The problem of gas-particle flow through a nozzle is solved using a first order finite difference scheme. A suitable stability condition for the numerical scheme for gas-particle flows is defined. Results obtained from the present set of equations are compared with those of the previous set of equations. It is also found that present set of equations give results which are in good agreement with the experimental observation.

Monte carlo simulation for molecular gas dynamics

The dynamics of low-density flows is governed by the Boltzmann equation of the kinetic theory of gases. This is a nonlinear integro-differential equation and, in general, numerical methods must be used to obtain its solution. The present paper, after a brief review of Direct Simulation Monte Carlo (DSMC) methods due to Bird, and Belotserkovskii and Yanitskii, studies the details of theDSMC method of Deshpande for mono as well as multicomponent gases. The present method is a statistical particle-in-cell method and is based upon the Kac-Prigogine master equation which reduces to the Boltzmann equation under the hypothesis of molecular chaos. The proposed Markoff model simulating the collisions uses a Poisson distribution for the number of collisions allowed in cells into which the physical space is divided. The model is then extended to a binary mixture of gases and it is shown that it is necessary to perform the collisions in a certain sequence to obtain unbiased simulation.

The physical properties of SnS films grown on lattice-matched and amorphous substrates

The development of high-quality tin monosulphide (SnS) layers is one of the crucial tasks in the fabrication of efficient SnS-based optoelectronic devices. Reduction of strain between film and the substrate by using an appropriate lattice-matched (LM) substrate is a new attempt for the growth of high-quality layers. In this view, the SnS films were deposited on LM Al substrate using the thermal evaporation technique with a low rate of evaporation. The as-grown SnS films were characterized using appropriate techniques and the obtained results are discussed by comparing them with the properties of SnS films grown on amorphous substrate under the same conditions. From structural analysis of the films, it is noticed that the SnS films deposited on amorphous substrate have crystallites that were oriented along different directions. However, the SnS crystallites grown on Al substrate exhibited epitaxial growth along the 101] direction. Photoluminescence (PL) and Raman studies reveal that the films grown on Al substrate have better optical properties than those of the films grown on amorphous substrates. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of FeCu Nanopowder by Levitational Gas Condensation Process

Condensation from the vapor state is an important technique for the preparation of nanopowders. Levitational gas condensation is one such technique that has a unique ability of attaining steady state. Here, we present the results of applying this technique to an iron-copper alloy (96Fe-4Cu). A qualitative model of the process is proposed to understand the process and the characteristics of resultant powder. A phase diagram of the alloy system in the liquid-vapor region was calculated to help understand the course of condensation, especially partitioning and coring during processing. The phase diagram could not explain coring in view of the simultaneous occurrence of solidification and the fast homogenization through diffusion in the nanoparticles; however, it could predict the very low levels of copper observed in the levitated drop. The enrichment of copper observed near the surface of the powder was considered to be a manifestation of the lower surface energy of copper compared with that of iron. Heat transfer calculations indicated that most condensed particles can undergo solidification even when they are still in the proximity of the levitated drop. It helped us to predict the temperature and the cooling rate of the powder particles as they move away from the levitated drop. The particles formed by the process seem to be single domain, single crystals that are magnetic in nature. They, thus, can agglomerate by forming a chain-like structure, which manifests as a three-dimensional network enclosing a large unoccupied space, as noticed in scanning electron microscopy and transmission electron microscopy studies. This also explains the observed low packing density of the nanopowders.

Search on a hypercubic lattice using a quantum random walk. I. d > 2

Random walks describe diffusion processes, where movement at every time step is restricted to only the neighboring locations. We construct a quantum random walk algorithm, based on discretization of the Dirac evolution operator inspired by staggered lattice fermions. We use it to investigate the spatial search problem, that is, to find a marked vertex on a d-dimensional hypercubic lattice. The restriction on movement hardly matters for d > 2, and scaling behavior close to Grover's optimal algorithm (which has no restriction on movement) can be achieved. Using numerical simulations, we optimize the proportionality constants of the scaling behavior, and demonstrate the approach to that for Grover's algorithm (equivalent to the mean-field theory or the d -> infinity limit). In particular, the scaling behavior for d = 3 is only about 25% higher than the optimal d -> infinity value.

Search on a hypercubic lattice using a quantum random walk. II. d = 2

We investigate the spatial search problem on the two-dimensional square lattice, using the Dirac evolution operator discretized according to the staggered lattice fermion formalism. d = 2 is the critical dimension for the spatial search problem, where infrared divergence of the evolution operator leads to logarithmic factors in the scaling behavior. As a result, the construction used in our accompanying article A. Patel and M. A. Rahaman, Phys. Rev. A 82, 032330 (2010)] provides an O(root N ln N) algorithm, which is not optimal. The scaling behavior can be improved to O(root N ln N) by cleverly controlling the massless Dirac evolution operator by an ancilla qubit, as proposed by Tulsi Phys. Rev. A 78, 012310 (2008)]. We reinterpret the ancilla control as introduction of an effective mass at the marked vertex, and optimize the proportionality constants of the scaling behavior of the algorithm by numerically tuning the parameters.

Support-Dependent Activity of Noble Metal Substituted Oxide Catalysts for the Water Gas Shift Reaction

The water gas shift reaction was carried out over noble metal ion substituted nanocrystalline oxide catalysts with different supports. Spectroscopic studies of the catalysts before and after the reaction showed different surface phenomena occurring over the catalysts. Reaction mechanisms were proposed based upon the surface processes and intermediates formed. The dual site mechanism utilizing the oxide ion vacancies for water dissociation and metal ions for CO adsorption was proposed to describe the kinetics of the reaction over the reducible oxides like CeO2. A mechanism based on the interaction of adsorbed CO and the hydroxyl group was proposed for the reaction over ZrO2. A hybrid mechanism based on oxide ion vacancies and surface hydroxyl groups was proposed for the reaction over TiO2. The deactivation of the catalysts was also found to be support dependent. Kinetic models for both activation and deactivation were proposed. (C) 2010 American Institute of Chemical Engineers AIChE J, 56: 2662-2676, 2010

Variational calculation for the spin-(1/2 Heisenberg antiferromagnet on a square lattice

The ground-state properties of the spin-(1/2 Heisenberg antiferromagnet on a square lattice are studied by using a simple variational wave function that interpolates continuously between the Néel state and short-range resonating-valence-bond states. Exact calculations of the variational energy for small systems show that the state with the lowest energy has long-range antiferromagnetic order. The staggered magnetization in this state is approximately 70% of its maximum possible value. The variational estimate of the ground-state energy is substantially lower than the value obtained for the nearest-neighbor resonating-valence-bond wave function.

Analysis of performance of a hot gas injection thrust vector control system

The complex three-dimensional flowfield produced by secondary injection of hot gases in a rocket nozzle for thrust vector control is analyzed by solving unsteady three-dimensional Euler equations with appropriate boundary conditions. Various system performance parameters like secondary jet amplification factor and axial thrust augmentation are deduced by integrating the nozzle wall pressure distributions obtained as part of the flowfield solution and compared with measurements taken in actual static tests. The agreement is good within the practical range of secondary injectant flow rates for thrust vector control applications.

Exploring glueball wave functions on the lattice

We calculate the string tension and 0++ and 2++ glueball masses in pure gauge QCD using an improved lattice action. We compare various smearing methods, and find that the best glueball signal is obtained using smeared Wilson loops of a size of about 0.5 fm. Our results for mass ratios m0++/√σ=3.5(3) and m2++/m0++=1.6(2) are consistent with those computed with the simple plaquette action.

Gas Sensing Characteristics of Superconducting Cuprates

Gas sensing characteristics of YBa2Cu3O7−δ, La2−x SrxCuO4, and Bi2Y1−xCaxSr2Cu2O8 have been examined. La2−x SrxCuO4 (x = 0.075), and Bi2YSr2Cu2O8 are found to show good sensitivity (≈10 ppm) to ethyl alcohol and such vapours.