A global approach to error estimation and physical diagnostics in multidimensional computational fluid dynamics

An approach for simultaneously assessing numerical accuracy and extracting physical information from multidimensional calculations of complex (engineering) flows is proposed and demonstrated. The method is based on global balance equations, i.e. volume-integrated partial differential equations for primary or derived physical quantities of interest. Balances can be applied to the full computational domain or to any subdomain down to the single-cell level. Applications to in-cylinder flows in reciprocating engines are used for illustration. It is demonstrated that comparison of the relative magnitude of the terms in the balances provides insight into the physics of the flow being computed. Moreover, for quantities that are not conserved at the cell or control volume level in the construction of the numerical scheme, the imbalance allows a direct assessment of numerical accuracy in a single run using a single mesh. The mean kinetic energy imbalance is shown to be a particularly sensitive indicator of numerical accuracy. This simple and powerful diagnostic approach can be implemented for finite-difference, finite-volume or finite-element methods.     

A Monte Carlo study of the thermal properties of Cu3Au low index surfaces

The thermal dependencies of composition and order of the (111), (100) and (110) Cu₃Au surfaces are studied at the atomic scale by means of Monte Carlo simulations in the “transmutational” ensemble at constant volume. The question addressed is the extent to which such simulations carried on with a model N-body potential designed on the basis of bulk energetic and mechanical properties allow predictions consistent with experimental observations of the surface. Although the currently available experimental data still leave unanswered questions, many of them allow for comparison with modelling. Qualitative agreement is found for temperature dependencies of both surface composition and order, and the simulation results are discussed in detail. Some clear discrepancies are found as well, in particular (but not only) in the case of the (110) surface and its first neighbouring layer. Although the origin of such differences is not yet clear, it is suggested that they may serve to assess and to improve the model in the light of quantitative surface studies.     

Photoisomerizable bipyridine ligands and macroligands: absorption, photoisomerization properties and theoretical study.

Two 2,2'-bipyridines, substituted at the 4,4'-positions by p-dialkylaminophenylazostyryl moieties p-R2N-C6H4-N=N-C6H4-CH=CH-[6 a, R2N=nBu2N; 6 b, R2N=(nBu)(C4H8OTHP)N; 6 c, R2N=(nBu)(C4H8OH)N], were successfully synthesized by using Wadworth-Emmons reactions. The X-ray structure of 6 a has been determined. Esterification of 6 c with 2-bromoisobutyroylbromide afforded 6 d. This ligand was used as an initiator for the living radical polymerization of methylmethacrylate (MMA) and gave rise to macroligand 6 e. Thin films of good optical quality were obtained by the spin-coating technique. Photoisomerization experiments were carried out on 6 a in solution and on 6 e in both solution and film, and the kinetics of photochemical (E/Z) and thermal (Z/E) isomerization were investigated. They were found to show Z-E back isomerization typical of aminoazobenzene-type rather than of push-pull-type molecules. Density functional theoretical (TD-DFT) calculations were performed on model compound 6 a' (R2N=Me2N) to understand the structural and electronic transitions of the corresponding E-E, E-Z and Z-Z isomers. It was found that the E-E isomer is almost planar as observed experimentally by X-ray diffraction, whereas the Z-Z isomer, which is 35.4 kcal mol(-1) less stable than the E-E isomer, is nonplanar. The theoretical studies also reveal that several transitions of pi-pi*, n-pi* and charge-transfer (CT) types, are involved in the long-wavelength transition of 6 a (E-E). The same observations can be made for the (Z-Z) isomer, and the TD-DFT simulated spectrum fits quite nicely to the experimental, reproducing and explaining the apparition of a blue-shifted charge-transfer band at 390 nm.     

Ab initio and DFT investigation of the structures and properties of chloromethyl and chlorofluoromethyl peroxyl radicals

Ab initio and Density Functional Theory (DFT) calculations were performed to determine the equilibrium geometries, charge distributions, spin density distributions, dipole moments, electron affinities (EAs), and C–O bond dissociation energies (BDEs) of CH₂ClO₂^? CHCl₂O₂^?, CCl₃O₂^?, CF₂ClO₂^?, CFCl₂O₂^?, and CHFClO₂^? peroxyl radicals. The C–H BDEs of the parent methanes were calculated using the same levels of theories. Both MP2(full) and B3LYP methods, using the 6‐31G(d,p) basis set, were found to be capable of accurately predicting the geometries of peroxyl radicals. The B3LYP/6‐31G(d,p) method was found to be comparable to high ab initio levels in predicting C–O BDEs of studied peroxyl radicals and C–H BDEs of the parent alkanes. The progressive chlorine substitution of hydrogen atoms in methyl peroxyl radicals results in an increase (decrease) of the spin density on the terminal (inner) oxygen, a decrease in dipole moments, and an increase in electron affinities. The substitution of fluorine by chlorine in the series CF₃O₂^? – CCl₃O₂^? was found to lengthen (destabilize) the C–O bonds. Both C–O BDEs and EAs of peroxyl radicals (RO₂^?) were found to correlate well with Taft σ* substituent constants for the R groups. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Carbon?hydrogen versus carbon?heteroatom activation by a high‐valent zirconium‐imido complex

A density functional theory (DFT) study of carbon? hydrogen versus carbon? heteroatom bond activation is presented. Heteroatom groups (X) investigated include X = F, Cl, OH, SH, NH₂, PH₂. The activating model complex is a prototypical d⁰ zirconium‐imide. While C? X activation has a thermodynamic advantage over C? H activation, the former has been found to have a kinetic advantage. Implications for catalytic hydrocarbon functionalization and phosphine–ligand degradation are discussed. The present results for a high‐valent metal complex are compared/contrasted with low‐valent bond activating complexes. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Aromatization of cyclohexadienes by TEMPO electro-mediated oxidation: Kinetic and structural aspects

Cyclohexadienes are easily converted into the corresponding aromatics in excellent yield (>90%) in the presence of 2,2,6,6-tetramethyl-1-oxopiperidinium ion (TEMPO⁺). The TEMPO radical was used in catalytic amount and was electrochemically regenerated in the presence of 2,6-lutidine as a base in hydro-organic medium (AcCN/H₂O 95/5). This work has been focused on the kinetic aspects. We have demonstrated that the reactivity of different cyclohexadienes is strongly dependent on the configuration of the double bonds and on the nature of the substituents. Competition between allylic functionalization and aromatization has been observed during the oxidation of 1,2-dihydro-4-phenylnaphthalene.     

Coupled fused silica capillaries for rapid capillary zone electrophoresis of proteins

A novel two-dimensional electrophoretic system for the control of electroosmosis in capillary zone electrophoresis has been developed and evaluated for rapid separations of proteins. The system comprises uncoated and polyether-coated fused silica capillaries coupled in series. An equation relating the average electroosmotic flow velocity in the coupled capillaries to the intrinsic electroosmotic velocities of the connected segments and their corresponding lengths has been derived and verified experimentally. This approach has the advantage of enabling the electroosmotic flow to be tuned independently of the applied voltage. As a consequence, rapid protein analysis at relatively low field strength was achieved without sacrificing the high separation efficiencies obtained with surface-modified capillaries.     

Synthesis of Some New Fused/Spiroheterocyclic Compounds Incorporating Quinone Compounds

A series of fused and spiro pyrazolones, isoxazolines, pyrimidines, β‐lactams, and thiazolidinones incorporating 4‐amino‐2‐methyl‐5,10‐dioxo‐1,5,10,11‐tetrahydrobenz[g]quinoline 3‐carbonitrile 1 and 4‐amino‐2‐methyl‐5,6,11‐trioxo‐1,4,4a,5,6,11,12,12a‐octahydro‐1,12‐diazanaphthacene 3‐carbonitrile 2. 7,8a‐c, 15,16a‐c, 19,20a‐d, 21,22a‐d , have been synthesised by cyclocondensation addition reaction and cycloaddition reaction of hydrazines, hydroxylamine, urea, thiourea, monochloroacetyl chloride and mercaptoacetic acid with the synthesised 15,16a‐c and 17,18a‐c .