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101.
Carlos M. Silva Poliana L. Silva Josefredo R. Pliego 《International journal of quantum chemistry》2014,114(8):501-507
Experimental kinetics of sulfide oxidation by hydrogen peroxide presents a pH‐dependent profile. In this article, it was carried out a detailed study of the mechanism and kinetics of dimethyl sulfide (DMS) oxidation by H2O2 in neutral, acid, and basic aqueous medium using ab initio calculations. The results point out that DMS oxidation in neutral aqueous medium occurs through its direct reaction with H2O2. In acid medium, cluster‐continuum model calculations shows that cluster is the best representation of the very reactive species. In basic medium, there is formation of the species. However, the pathway involving this species has high free energy barrier, making this pathway unfeasible. The theoretical pH‐rate profile is in good agreement with the experimental observations. © 2013 Wiley Periodicals, Inc. 相似文献
102.
Carlos Chiquete Mark Short Chad D. Meyer James J. Quirk 《Combustion Theory and Modelling》2018,22(4):744-776
An approach for the calibration of an advanced programmed burn (PB) model for detonation performance calculations in high explosive systems is detailed. Programmed burn methods split the detonation performance calculation into two components: timing and energy release. For the timing, the PB model uses a Detonation Shock Dynamics (DSD) surface propagation model, where the normal surface speed is a function of local surface curvature. For the energy release calculation and subsequent hydrodynamic flow evolution, a Pseudo-Reaction-Zone (PRZ) model is used. The PRZ model is similar to a reactive burn model in that it converts reactants into products at a finite rate, but it has a reaction rate dependent on the normal surface speed derived from the DSD calculation. The PRZ reaction rate parameters must be calibrated in such a way that the rate of energy release due to reaction in multi-dimensional geometries is consistent with the timing calculation provided by the DSD model. Our strategy for achieving this is to run the PRZ model in a detonation shock-attached frame in a compliant 2D planar slab geometry in an equivalent way to a reactive burn model, from which we can generate detonation front shapes and detonation phase speed variations with slab thickness. In this case, the D n field used by the PRZ model is then simply the normal detonation shock speed rather than the DSD surface normal speed. The PRZ rate parameters are then iterated on to match the equivalent surface front shapes and surface phase speed variations with slab thickness derived from the target DSD model. For the purposes of this paper, the target DSD model is fitted to the performance properties of an idealised condensed-phase reactive burn model, which allows us to compare the detonation structure of the calibrated PRZ model to that of the originating idealised-condensed phase model. 相似文献
103.
We investigate the spin-orbit (SO) interaction in two-dimensional electron gases in quantum wells with two subbands. From the 8x8 Kane model, we derive a new intersubband-induced SO term which resembles the functional form of the Rashba SO but is nonzero even in symmetric structures. This follows from the distinct parity of the confined states (even or odd) which obliterates the need for asymmetric potentials. We self-consistently calculate the new SO coupling strength for realistic wells and find it comparable to the usual Rashba constant. Our new SO term gives rise to a nonzero ballistic spin-Hall conductivity, which changes sign as a function of the Fermi energy (epsilonF) and can induce an unusual Zitterbewegung with cycloidal trajectories without magnetic fields. 相似文献
104.
Cobalt-substituted ferrite nanoparticles were synthesized with a narrow size distribution using reverse micelles formed in the system water/AOT/isooctane. Fe:Co ratios of 3:1, 4:1, and 5:1 were used in the synthesis, obtaining cobalt-substituted ferrites (CoxFe3−xO4) and some indication of γ-Fe3O4 when 4:1 and 5:1 Fe:Co ratios were used. Inductively coupled plasma mass spectroscopy (ICP-MS) verified the presence of cobalt in all samples. Fourier transform infrared (FTIR) showed bands at ∼560 and ∼400 cm−1, characteristic of the metal–oxygen bond in ferrites. Transmission electron microscopy showed that the number median diameter of the particles was ∼3 nm with a geometric deviation of ∼0.2. X-ray diffraction (XRD) confirmed the inverse spinel structure typical of ferrites with a lattice parameter of a=8.388 Å for Co0.61Fe0.39O4, which is near that of CoFe2O4 (a=8.394 Å). Magnetic properties were determined using a superconducting quantum interference device (SQUID). Coercivities higher than 8 kOe were observed at 5 K, whereas at 300 K the particles showed superparamagnetic behavior. The anisotropy constant was determined based on the Debye model for a magnetic dipole in an oscillating field and an expression relating χ′ and the temperature of the in-phase susceptibility peak. Anisotropy constant values in the order of ∼106 erg/cm3 were determined using the Debye model, whereas anisotropy constants in the order of ∼107 erg/cm3 were calculated assuming Ωτ=1 at the temperature peak of the in-phase component of the susceptibility curve as commonly done in the literature. Our analysis demonstrates that the assumption Ωτ=1 at the temperature peak of χ′ is rigorously incorrect. 相似文献
105.
Avila-Brande D Urones-Garrote E Katcho NA Lomba E Gómez-Herrero A Landa-Cánovas AR Carlos Otero-Díaz L 《Micron (Oxford, England : 1993)》2007,38(4):335-345
In this work we report some new well-defined carbon nanostructures produced by direct chlorination of metallocenes (ferrocene and cobaltocene) and NbC, at temperatures from 100 to 900 degrees C. Thus, amorphous carbon nanotubes with variable dimensions depending on reaction temperature were produced from ferrocene. When cobaltocene is the carbon precursor the main product are solid amorphous nanospheres. The high refractory metal carbide NbC as carbon source favours the growth of nanospherical cabbage-like particles with a higher degree of graphene sheets order. Besides, NbC crystallites encapsulated in an amorphous carbon shell were also found at lower temperatures (T< or =700 degrees C). 相似文献
106.
Inaccuracies in the calibration of a stereoscopic system appear with errors in point correspondences between both images and inexact points localization in each image. Errors increase if the stereoscopic system is composed of wide angle lens cameras. We propose a technique where detected points in both images are corrected before estimating the fundamental matrix and the lens distortion models. Since points are corrected first, errors in point correspondences and point localization are avoided. To correct point location in both images, geometrical and epipolar constraints are imposed in a nonlinear minimization problem. Geometrical constraints define the point localization in relation to its neighbors in the same image, and eipolar constraints represent the location of one point referred to its corresponding point in the other image. 相似文献
107.
Rössler E Mattea C Mollova A Stapf S 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2011,213(1):112-118
The structure of articular cartilage is separated into three layers of differently oriented collagen fibers, which is accompanied by a gradient of increasing glycosaminoglycan (GAG) and decreasing water concentration from the top layer towards the bone interface. The combined effect of these structural variations results in a change of the longitudinal and transverse relaxation times as a function of the distance from the cartilage surface. In this paper, this dependence is investigated at a magnetic field strength of 0.27 T with a one-dimensional depth resolution of 50 μm on bovine hip and stifle joint articular cartilage. By employing this method, advantage is taken of the increasing contrast of the longitudinal relaxation rate found at lower magnetic field strengths. Furthermore, evidence for an orientational dependence of relaxation times with respect to an axis normal to the surface plane is given, an observation that has recently been reported using high-field MRI and that was explained by preferential orientations of collagen bundles in each of the three cartilage zones. In order to quantify the extent of a further contrast mechanism and to estimate spatially dependent glycosaminoglycan concentrations, the data are supplemented by proton relaxation times that were acquired in bovine articular cartilage that was soaked in a 0.8 mM aqueous Gd++ solution. 相似文献
108.
109.
Juan Carlos De los Reyes Sergio González Andrade 《Journal of Computational and Applied Mathematics》2010,235(1):11-32
This paper is devoted to the numerical simulation of two-dimensional stationary Bingham fluid flow by semismooth Newton methods. We analyze the modeling variational inequality of the second kind, considering both Dirichlet and stress-free boundary conditions. A family of Tikhonov regularized problems is proposed and the convergence of the regularized solutions to the original one is verified. By using Fenchel’s duality, optimality systems which characterize the original and regularized solutions are obtained. The regularized optimality systems are discretized using a finite element method with (cross-grid P1)-Q0 elements for the velocity and pressure, respectively. A semismooth Newton algorithm is proposed in order to solve the discretized optimality systems. Using an additional relaxation, a descent direction is constructed from each semismooth Newton iteration. Local superlinear convergence of the method is also proved. Finally, we perform numerical experiments in order to investigate the behavior and efficiency of the method. 相似文献
110.
Simonetta Frittelli Carlos Kozameh Ezra T. Newman 《Communications in Mathematical Physics》2001,223(2):383-408
We first show how, from the general 3rd order ODE of the form , one can construct a natural Lorentzian conformal metric on the four-dimensional space . When the function satisfies a special differential condition the conformal metric possesses a conformal Killing field, , which in turn, allows the conformal metric to be mapped into a three dimensional Lorentzian metric on the space ) or equivalently, on the space of solutions of the original differential equation. This construction is then generalized
to the pair of differential equations, z
ss
=S(z,z
s
,z
t
,z
st
,s,t) and z
tt
=T(z,z
s
,z
t
,z
st
,s,t), with z
s
and z
t
the derivatives of z with respect to s and t. In this case, from S and T, one can again, in a natural manner, construct a Lorentzian conformal metric on the six dimensional space (z,z
s
,z
t
,z
st
,s,t). When the S and T satisfy differential conditions analogous to those of the 3rd order ode, the 6-space then possesses a pair of conformal Killing fields, and which allows, via the mapping to the four-space of (z,z
s
,z
t
,z
st
) and a choice of conformal factor, the construction of a four-dimensional Lorentzian metric. In fact all four-dimensional
Lorentzian metrics can be constructed in this manner. This construction, with further conditions on S and T, thus includes all (local) solutions of the Einstein equations.
Received: 10 October 2000 / Accepted: 26 June 2001 相似文献