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  • 1995-1999  (2,863)
  • 1920-1924
  • Theoretical, Physical and Computational Chemistry  (1,576)
  • Numerical Methods and Modeling  (1,287)
  • 101
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 11 (1998), S. 55-68 
    ISSN: 0894-3370
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: Multiresolution time domain (MRTD) analysis is applied directly to Maxwell's equations to model inhomogeneous dielectric material. In our approach, scaling and wavelet functions are used as a complete basis for the method of moments. The MRTD scheme is used to analyze different types of resonant cavity structures with varying dielectric perturbations in one, two and three dimensions. The results presented here agree very well with those obtained by FDTD, FEM and integral equation methods. MRTD allows for considerable savings in memory and computation time in comparison to FDTD, while maintaining the same accuracy of the results. © 1998 John Wiley & Sons, Ltd.
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  • 102
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 11 (1998), S. 1-1 
    ISSN: 0894-3370
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: No Abstract
    Type of Medium: Electronic Resource
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  • 103
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 11 (1998), S. 105-121 
    ISSN: 0894-3370
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: This paper describes a computationally efficient diakoptic algorithm for the solution of closed-mesh electrical network equations. The algorithm is designed for use with time-varying and/or discontinuous equations describing limited size power supply systems, allowing them to be torn into smaller subdivisions in a manner that is independent of their structure. The efficiency of the algorithm is demonstrated by comparing its performance with that obtained when using a more conventional sparse matrix technique, on the basis of the number of floating point operations required for the solution of a range of typical network problems. Mention is made of the parallel processes inherent in the resultant equation structure. © 1998 John Wiley & Sons, Ltd.
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  • 104
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 11 (1998), S. 207-219 
    ISSN: 0894-3370
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: The IMPETUS II code simulates the atomic mixing and particle emission that occurs when a solid is bombarded by energetic particles (as in SIMS or SNMS). The underlying model consists of a system of partial differential equations that are solved by a finite difference method (FDM). Special techniques are also employed to model thin layers and sharp interfaces, to deal efficiently with wide homogeneous layers (when the solution is tending to a steady state), to model linear diffusion in order to smooth the sharp interfaces before they enter to domain of the FDM.In this paper the special techniques are described in detail. Results from test problems, demonstrating these techniques, are shown. An algorithm that describes the way the IMPETUS II code is structured is given. © 1998 John Wiley & Sons, Ltd.
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  • 105
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 11 (1998), S. 221-229 
    ISSN: 0894-3370
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: This paper presents a physical-mathematical model for abrupt heterojunction transistors and its solution using numerical methods with application to InP/InGaAs HBTs. The physical model is based on the combination of the drift-diffusion transport model in the bulk with thermionic emission and tunnelling transmission through the emitter-base interface. Fermi-Dirac statistics and bandgap narrowing distribution between the valence and conduction bands are considered in the model. A compact formulation is used that makes it easy to take into account other effects such as the non-parabolic nature of the bands or the presence of various subbands in the conduction process. The simulator has been implemented for distributed memory multicomputers, making use of the MPI message-passing standard library. In order to accelerate the solution process of the linear system, iterative methods with parallel incomplete factorization-based preconditioners have been used. © 1998 John Wiley & Sons, Ltd.
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  • 106
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 11 (1998), S. 273-273 
    ISSN: 0894-3370
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: No Abstract
    Type of Medium: Electronic Resource
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  • 107
    Electronic Resource
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    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 11 (1998), S. 233-242 
    ISSN: 0894-3370
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: The propagation factors of buried microstrip lines are considered. The associated eigenvalue problems are solved by the edge-based vectorial finite element method (VFEM). To improve the higher-order VFEM solutions, the problem infinite domain is truncated by second-order absorbing boundary conditions (ABCs). This reduces the number of unknowns and, consequently, the numerical effort. Owing to the many advantages of both the edge-based VFEM and the second-order ABCs, this full-wave method is implemented by a general computer program for solving unbounded domain problems involving complex geometries and inhomogeneous media. The examples presented show the validity of this technique. © 1998 John Wiley & Sons, Ltd.
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  • 108
    Electronic Resource
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    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 11 (1998), S. 243-254 
    ISSN: 0894-3370
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: Various local absorbing boundary conditions are implemented in the TLM method and their corresponding reflections are compared as a waveguide termination. The instability in different ABCs is discussed and reflections from the terminating walls are computed. An improvement for the matched termination wall is proposed and reflection of this absorbing condition is compared with ordinary matched termination. © 1998 John Wiley & Sons, Ltd.
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  • 109
    Electronic Resource
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    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 11 (1998), S. 317-318 
    ISSN: 0894-3370
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: No Abstract
    Type of Medium: Electronic Resource
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  • 110
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 11 (1998), S. 289-298 
    ISSN: 0894-3370
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: Oscillatory flow present in the melt during InSb single crystal growth using an RF-heating Czochralski method has been numerically investigated by means of the finite difference method using the HSMAC algorithm. The thermal boundary conditions required for the numerical simulation model were obtained experimentally by measuring the temperature profile along the crucible of a Czochralski system by means of thermocouples mounted in the crucible. Results of numerical simulations showed that the use of a third-order upwind discretization scheme was necessary to catch the oscillatory behaviour of the fluid flow in the melt. It was shown that this oscillatory behaviour strongly depends on the crystal rotation rate. Indeed, the oscillation period increases when the crystal rotation rate is above a critical rotation rate. In order to avoid such oscillations, crystal rotation rates lower than this critical value of crystal rotation rate must be selected for the growth of high quality crystals free of striations. © 1998 John Wiley & Sons, Ltd.
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  • 111
    Electronic Resource
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    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 11 (1998), S. 299-306 
    ISSN: 0894-3370
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: The application of the FDTD algorithm on generalized non-orthogonal meshes, following the basic ideas of Holland (1983), has been investigated by many authors for several years now, and detailed dispersion analysis as well as convergence studies have been published. Already in 1992 also a general stability criterion was given for the time integration using the standard leap-frog scheme (Lee et al.). Many authors, however, still propose some damped time stepping algorithms to work around unexpected instabilities in the discretization method. In this paper the origin of this type of instability is revealed, and a technique to obtain a stable discretization of Maxwell's equations on non-orthogonal grids is proposed. To obtain more insight into the stability properties of the method, it is reformulated according to the matrix-vector notation of the Finite Integration Technique. © 1998 John Wiley & Sons, Ltd.
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  • 112
    ISSN: 0894-3230
    Keywords: lanthanide ion ; hydrolysis ; α-amino acid esters ; α-amino acid amides ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Lanthanide ion-induced hydrolyses of methyl esters, ethyl esters, and amides of α-amino acids were systematically studied. In the hydrolysis of the alkyl esters, all the lanthanide ions are effective and the catalytic activities decrease in the order Ce(III), Nd(III) 〉 Sm(III) 〉 Eu(III) 〉 Gd(III), Ce(IV) 〉 Pr(III) 〉 Dy(III), Tb(III), Er(III), Ho(III), Tm(III) 〉 La(III), Lu(III), Yb(III). For the hydrolysis of the amides, however, the Ce(IV) ion is overwhelmingly more active than other lanthanide(III) and non-lanthanide ions. The results are interpreted in terms of the difference in the rate-limiting step for these two reactions. © 1998 John Wiley & Sons, Ltd.
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  • 113
    ISSN: 0894-3230
    Keywords: alkyltrimethylammonium bromides ; sodium alkylsulphates ; partial molar volumes ; partial molar isentropic compressibilities ; hydration ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Density and sound velocity data for aqueous solutions at 298.2 K containing alkyltrimethylammonium bromides and sodium alkylsulphates were analysed to yield partial molar volumes and isentropic compressions. The calculated contributions of methylene groups to the properties of alkyltrimethylammonium cations and alkylsulphate anions show no dependence on position in the alkyl chains and a common contribution to the ionic partial molar volumes over the range methyl ≤ n-octyl for the sulphates and n-propyl ≤ n-hexyl for the alkyltrimethylammonium ions. However, a switch in head group from trimethylammonium to sulphate changes the contribution of methylene groups to estimated partial molar isentropic compressibilities. The reasons for this sensitivity are discussed in terms of hydration characteristics. © 1998 John Wiley & Sons, Ltd.
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  • 114
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 763-773 
    ISSN: 0894-3230
    Keywords: 1-azabicycl[1.1.0]butyl cations ; 3-azetidinyl cations ; aziridinylmethyl cations ; ab initio ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvolysis products of 3-azetidinyl chlorides, tosylates, and mesylates have been interpreted previously to indicate that these reactions proceed by azabicyclo[1.1.0]butyl cationic intermediates. Whether these cations are formed by direct ionization to 3-azetidinyl cations followed by collapse to the bicyclic ion or are formed with anchimeric assistance by the lone pair of electrons on nitrogen is unclear. This investigation was initiated to assess the relative stability of these bicyclic cations and their isomeric 3-azetidinyl and aziridinylmethyl cations. All ab initio methods investigated suggest that the bicyclic ions (1) are much more stable than the corresponding 3-azetidinyl cations (3) and that transition states for conversion of the bicyclic ions to azetidinyl carbocations are not acheivable from the bicyclic ions. Hartree-Fock ab initio calculations on N-methyl (and N,2-dimethyl) bicyclic ions and their isomeric aziridinylmethyl cations (2) indicate that the bicyclic ions are significantly more stable than are the isomeric partially ring-opened cations, and that transition states (4) for conversion of the bicyclic ions to the corresponding aziridinylmethyl carbocations are probably energetically unattainable. Hartree-Fock theory predicts that the N-methyl-2-phenylbicyclic ions are slightly less stable than the resulting aziridinylmethyl cations. Calculations which include electron correlation (MP2) indicate, however, that all bicyclic ions investigated are more stable than any of their isomeric carbocations. © 1998 John Wiley & Sons, Ltd.
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  • 115
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 787-792 
    ISSN: 0894-3230
    Keywords: nucleophilic aromatic substitution ; Meisenheimer complexes ; nucleophilic reactivity ; trinitro-aromatics ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Kinetic and equilibrium results are reported for the reactions of sulphite with the ethyl and phenyl ethers of 2,4,6-trinitrophenol and 2,4,6-trinitrothiophenol in 80/20 (v/v) water/DMSO. In each case 1:1 and 1:2 adducts are observed by reaction of sulphite at one or two unsubstituted ring positions respectively. In the case of the ethyl derivatives these adducts are long-lived however, the phenyl derivatives rapidly yield 2,4,6-trinitrobenzenesulphonate, the substitution product. This difference is attributed to a change in the nature of the rate-determining step, from nucleophilic attack with the phenyl derivatives to leaving group departure with the alkyl derivatives. © 1998 John Wiley & Sons, Ltd.
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  • 116
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 793-802 
    ISSN: 0894-3230
    Keywords: aldolase ; slow-binding inhibition ; enzyme affinity ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Compounds similar in structure to reactants, intermediates and products of the aldolase-catalysed reaction were synthesized and their affinities for the enzyme determined. The best situations were found with β-dicarbonyl phosphorylated compounds which are a good mimics of the incoming groups in the bond-forming process; the corresponding binding is characterized by slow-binding inhibition type, the inhibitors forming stabilized iminium ions and enamines with the enzyme; similar effects were obtained with an aromatic aldehyde, also capable of forming a stabilized iminium ion. The use of aldolase mutants allows one to characterize the lysyl group involved in the process and also to suggest a proton transfer mechanism for the iminium ion formation with the enzyme natural substrate. © 1998 John Wiley & Sons, Ltd.
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  • 117
    ISSN: 0894-3230
    Keywords: 1,2,5-thiadiazole ; 1,1-dioxide derivatives ; single-crystal x-ray diffraction ; ab initio MO calculations ; structure ; conformation ; reactivity ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Single-crystal x-ray diffraction studies are reported for 3,4-dimethyl (I), 3-methyl-4-phenyl (II) and 3,4-diphenyl (III) derivatives of 1,2,5-thiadiazole 1,1-dioxide. Ab initio MO calculations on the electronic structure, conformation and reactivity of I, II and III are also reported and compared with the x-ray results. The structural data are related to previous kinetic and electrochemical experimental results on these compounds. © 1998 John Wiley & Sons, Ltd.
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  • 118
    ISSN: 0894-3230
    Keywords: 4-formyl-, methyl- and -vinylcyclohexene ; stereodynamics ; conformation ; dynamic NMR ; molecular mechanics ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The 1H and 13C{1H} NMR spectra of 4-formylcyclohexene in 50% CF2Cl2-50% CHF2Cl decoalesce at very low temperatures and, at 108 K, have sharpened into a major (77%) and a minor (23%) subspectrum. Based on the NMR spectra and molecular mechanics calculations, the major subspectrum is assigned to a family of equatorial conformations and the minor subspectrum to a family of axial conformations. The free energy of activation for conversion of the equatorial conformations to the axial forms is 5.6 kcal mol-1 (1 kcal  =  4.184 kJ) at 117 K. Within a family of conformations, interconversion occurs rapidly at 108 K via formyl group rotation. The conformational preference in 4-formylcyclohexene is solvent dependent. In 50% CF2Cl2-50% CHF2Cl, CHF2Cl and CF2Cl2, the respective ratios of equatorial to axial conformations are 77:23, 77:23, and 89:11 at 108 K. The 1H and 13C{1H} NMR spectra of 4-methylcyclohexene and 4-vinylcyclohexene in 50% CF2Cl2-50% CHF2Cl show no evidence of decoalescence at very low temperatures but do show differential broadening and subsequent sharpening of various resonances characteristic of exchange between strongly dominant equatorial conformations and axial conformations present at too low a concentration to be detectable by NMR. A lower limit on the free energy preference for the equatorial conformations is estimated to be 1.0 kcal mol-1. Molecular mechanics calculations also predict a stronger preference for equatorial conformations in 4-methylcyclohexene and 4-vinylcyclohexene than in 4-formylcyclohexene. © 1998 John Wiley & Sons, Ltd.
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  • 119
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    Journal of Physical Organic Chemistry 11 (1998), S. 299-304 
    ISSN: 0894-3230
    Keywords: molecular architecture ; molecule-based magnets ; biopolymers ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Application of the principles of physical organic chemistry to the construction of molecule-based magnets is discussed. Not only the magnetic structures of conventional magnets but also secondary and tertiary structures of biopolymers are instrumental in the molecular design. © 1998 John Wiley & Sons, Ltd.
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  • 120
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    Journal of Physical Organic Chemistry 11 (1998), S. 350-355 
    ISSN: 0894-3230
    Keywords: 1,3-dipoles ; cumulenes ; infrared spectroscopy ; mass spectrometry ; flash vacuum thermolysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the direct investigation of reactive intermediates it is particularly valuable to use a combination of several spectroscopic techniques. This commentary highlights recent examples, using primarily flash vacuum thermolysis for the generation of the intermediates, and matrix IR spectroscopy in conjunction with gas-phase mass spectrometric methods for their identification. The examples include nitrile imines, nitrile ylides, nitrile sulfides and selenides, dinitrogen sulfide and several novel cumulenes (X=C=C=Y, RN=C=C=C=X). © 1998 John Wiley & Sons, Ltd.
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  • 121
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    Journal of Physical Organic Chemistry 11 (1998), S. 871-878 
    ISSN: 0894-3230
    Keywords: laticyclic hyperconjugation ; isodrin ; solvolysis ; through-bond and through-space interactions ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Enhanced rates of solvolysis have been reported for some isodrin derivatives, e.g. compounds 2, 3, 6 and 7 compared with anti-7-norbornene (1). The effect has been ascribed to the formation of laticyclic (2 + 2 + 0) π-delocalization on a carbocation such as 5. However, comparable rates of solvolysis were also observed for analogous monoenes 4, 8, 9 and 12, where no adequate explanation has been provided. Molecular modeling at both semiempirical and ab initio levels shows a good correlation between the stabilization energy of the cations and their kinetic data. The enhanced rate of solvolysis for 4, 8, 9 and 12 can be rationalized by strong effects of σ-bond participation in the transition state. For both series of compounds, the stabilization effect can be effectively transmitted either through space or through bonds. Copyright © 1998 John Wiley & Sons, Ltd.
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  • 122
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    Journal of Physical Organic Chemistry 11 (1998), S. 597-601 
    ISSN: 0894-3230
    Keywords: rhodium(II)-catalyzed nitrene transfer ; phenyliodonium ylides ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The [Rh2(OAc)4]-catalyzed decomposition of NsN=IPh {[N-(p-nitrobenzenesulfonyl)imino]phenyliodinane} affords aziridines in the presence of olefins and insertion products with compounds having activated CH bonds. The aziridination is stereospecific, and the insertion proceeds with retention of configuration. With chiral Rh(II) complexes, enantioenriched products result. A one-step mechanism involving a metal-complexed nitrene is proposed for both reactions. © 1998 John Wiley & Sons, Ltd.
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  • 123
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    Journal of Physical Organic Chemistry 11 (1998), S. 632-641 
    ISSN: 0894-3230
    Keywords: proton transfer reactions ; rate prediction ; equilibrium constants ; distortion energies ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple model for the energy surface of a reacting system permits the calculation of the free energies of activation. A chemical reaction is analyzed in terms of the simple processes (bond making/breaking or atom transfer; geometry changes) which must take place to achieve the overall transformation. When only one (or two, or three, …) of these processes has progressed to the full extent required for reaction, one has a ‘corner intermediate.’ The reaction diagram is viewed as a square (2D) or cube (3D) or hypercube (4D), etc., and energies at intermediate points on the energy surface or hypersurface are calculated by interpolation. Suitable equations have been obtained for this purpose. Along any section parallel to an axis the energy is given by an upward opening parabola centered at the lower energy end. This paper deals with the application of these ideas to proton transfer reactions involving carbon acids. For mono- or dicarbonyl compounds, with pKas ranging from 7 to 25.6, and rate constants for water or hydroxide ranging from 10-9.3 to 104.6, rate constants can be predicted with an r.m.s. error in log k of 0.99 for 51 reactions. © 1998 John Wiley & Sons, Ltd.
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  • 124
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    Journal of Physical Organic Chemistry 11 (1998), S. 540-545 
    ISSN: 0894-3230
    Keywords: metallodendrimers ; molecularly thin films ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A non-covalent synthesis route to assemble metallodendrimers was extended to the fifth generation. Generation four (G4) was characterized by electrospray mass spectrometry. Thin films of generation five (G5) metallodendrimers were studied by tapping mode scanning force microscopy. Both on graphite and on mica spherical particles with a diameter of ca 15 nm were observed. © 1998 John Wiley & Sons, Ltd.
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  • 125
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    Journal of Physical Organic Chemistry 11 (1998), S. 536-539 
    ISSN: 0894-3230
    Keywords: enzyme design ; enzyme mechanism ; genetic engineering ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Aspartate aminotransferase (AATase) and aminocyclopropane carboxylate synthase (ACC synthase) are pyridoxal phosphate (PLP)-dependent enzymes whose common junction of mechanistic divergence is after the formation of a Cα carbanion from the amino acid substrate bound to PLP as a Schiff base (aldimine). AATase catalyzes the reversible interconversion of α-amino acids and α-keto acids, while ACC synthase effects the irreversible decomposition of S-adenosylmethionine (SAM) to 1-aminocyclopropane-1-carboxylate (ACC) and 5′-methylthioadenosine (MTA). ACC is subsequently converted to ethylene, the plant ripening and senescence hormone, by ACC oxidase, the next enzyme in the pathway. AATase and ACC synthase exhibit many similar phenomenological characteristics that result from different detailed mechanistic origins. The kcat/KM versus pH profiles for both enzymes are similar (AATase, acidic pKa = 6.9, basic pKa = 9.6; ACC synthase, acidic pKa = 7.5, basic pKa = 8.9); however the acidic pKa of AATase reflects the ionization of an enzyme proton from the internal Schiff base, and the basic one is that of the α-amino group of the substrate, while the opposite situation obtains for ACC synthase, i.e. the apparent pKa of 7.4 is due to the α-amino group of SAM, whereas that of 9 reflects the Schiff base pKa. The mechanistic imperative underlying this reversal is dictated by the reaction mechanism and the low pKa of the α-amino group of SAM. The low pKa of SAM requires that the enzyme pKa be moved upward in order to have sufficient quantities of the reacting species at neutral pH. It is shown by viscosity variation experiments with wild-type and active site mutant controls of both enzymes that the reaction of SAM with ACC synthase is 100% diffusion controlled (kcat/KM = 1.2 × 106 l mol-1 s-1) while the corresponding reaction for the combination of L-aspartate with AATase is insensitive to viscosity, and is therefore chemically not diffusion limited. Tyr225 (AATase) or Tyr233 (ACC synthase) forms a hydrogen bond with the PLP in both enzymes, but that formed with the former enzyme is stronger and accounts for the lower pKa of the Schiff base. © 1998 John Wiley & Sons, Ltd.
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  • 126
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    Journal of Physical Organic Chemistry 11 (1998), S. 655-662 
    ISSN: 0894-3230
    Keywords: pericyclic reaction transition structures ; aromaticity ; magnetic susceptibility ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The transition states of thermally allowed pericyclic reactions are aromatic. They not only have highly delocalized structures and large resonance stabilizations (energies of concert), but also strongly enhanced magnetic susceptibilities (Λ) and appreciable NICS (nucleus-independent chemical shifts) values arising from the diatropic ring currents. Aromaticity is the consequence of cyclic electron delocalization, which can have σ and hybrid, and not just π character. © 1998 John Wiley & Sons, Ltd.
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  • 127
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    Journal of Physical Organic Chemistry 11 (1998), S. 589-596 
    ISSN: 0894-3230
    Keywords: intermediates ; spectroscopy ; polymers ; hydrogenation ; supercritical fluids ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: IR spectroscopy has transformed the study of mechanistic organometallic chemistry. Reaction intermediates can now be detected and characterized; their kinetics can be measured and their behaviour understood. However, the field is not static. New techniques are still being developed. We focus here on hydrogenation and related reactions describing (i) a miniature low-temperature/high-pressure cell, which allows photochemical reactions to be studied under high pressures of gases, (ii) the use of flow reactors for continuous reactions in supercritical fluids, including hydrogenation of organic compounds, and (iii) the use of supercritical fluid solutions for studying weak metal-ligand interactions by nanosecond time-resolved IR spectroscopy (TRIR) and the application of TRIR to the detection of intermediates in organic reactions. © 1998 John Wiley & Sons, Ltd.
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  • 128
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    Journal of Physical Organic Chemistry 11 (1998), S. 505-507 
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 129
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    Journal of Physical Organic Chemistry 11 (1998), S. 377-377 
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No abstract.
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  • 130
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    Journal of Physical Organic Chemistry 11 (1998), S. 419-425 
    ISSN: 0894-3230
    Keywords: 5-nitro-5′-dimethylamino-2,2′-bisthiophene ; π* probe dye ; cyclic voltammetry ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cyclic voltamograms of the solvatochromic dye 5-nitro-5′-dimethylamino-2,2′-bisthiophene (1), introduced recently as a sensitive π* probe, were recorded in different solvents. An EPR spectrum of the anionic radical of 1 in DMSO was obtained and compared with other spectra of analogous substituted bisthiophene radicals. It was found that the presence of a donor- acceptor pair of substituents in 1-⋅ reduces significantly the rotational barrier of the radical compared with the unsubstituted bithienyl radical anion 2-⋅. This is the result of an electronic repulsion between the donor ring fragment and the added electron in the coplanar radical, which does not exist in 2-⋅. © 1998 John Wiley & Sons, Ltd.
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  • 131
    ISSN: 0894-3230
    Keywords: calixarene sulphonates ; amino acids ; proteins ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The interactions of calixarene sulphonates with the basic amino acids arginine and lysine were studied by 1H NMR spectroscopy. Strong electrostatic binding occurs for calix[4]arene sulphonate with both lysine and arginine at pH 1 and 5. For the higher calixarenes, only weak interactions at the faces of the flattened macrocycles occur. This binding is in contrast to the inhibition of protein-protein interactions by the calixarenes where the calix[6]arene and calix[8]arene sulphonates show much stronger effects. © 1998 John Wiley & Sons, Ltd.
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  • 132
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    Journal of Physical Organic Chemistry 11 (1998), S. 715-721 
    ISSN: 0894-3230
    Keywords: unsaturated nitriles ; homolytic reactions ; cyclization ; tert-butylmercury halides ; proton donors ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cyclizations are observed in the homolytic reactions of t-BuHgI with CH2=CHCH2YCH2CN [Y = CH2, O, CMe2, C(CO2Et)2, NCH2CN] and CH2=CHCH2CH2YCH2CN [Y = CH2, O, C(CO2Et)2] in Me2SO in the presence of hydriodic acid. Only with Y = C(CO2Et)2 does the adduct radical, t-BuCH2ĊHCH2YCH2CN, undergo facile 5-exo cyclization in the absence of a proton donor. The other 5-exo and all 6-exo cyclizations require substrate protonation to yield t-BuCH2ĊH(CH2)nYCH2C≡NH+ (n = 1, 2), which cyclizes readily to the iminium radical cation followed by electron transfer with I- or t-BuHgI2- to form the imine as a precursor to the cyclopentanone or cyclohexanone upon hydrolysis. For CH2=CHCH2C(CO2Et)2CH2CN the formation of the cyclopentanone is dramatically promoted by NH4I in the dark in the absence of any other acid. In this case, where cyclization of the adduct radical occurs readily without substrate activation, protonation of the cyclized iminyl radical allows the electron transfer with I- or t-BuHgI2- to occur with regeneration of t-Buċ. A similar effect is observed with CH2=CHCH2C(CO2Et)2CH2N3 where only a slow reaction is observed upon photolysis with t-BuHgI in the absence of NH4I, although apparently cyclization of t-BuCH2ĊHCH2C(CO2Et)2CH2N3 (with loss of N2) occurs readily. In the presence of NH4I the cyclized aminyl radical can be protonated and the resulting amine radical cation readily reduced by I- or t-BuHgI2- to continue a chain process. With the thioesters CH2=CHCH2YCH2C(O)SPh [Y = O, CH2, CMe2, C(CO2Et)2], significant cyclization upon photolysis with t-BuHgX occurred only for Y = C(CO2Et)2. © 1998 John Wiley & Sons, Ltd.
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  • 133
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    Journal of Physical Organic Chemistry 11 (1998), S. 895-902 
    ISSN: 0894-3230
    Keywords: 1-amino-2,4-dinitrobenzenes ; structures ; single-crystal x-ray diffraction ; UV-visible spectrophotometry ; NMR spectroscopy ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal structures of 1-pyrrolidino-2,4-dinitrobenzene (3) and 1-morpholino-2,4-dinitrobenzene (4) were determined by single-crystal x-ray diffraction and the structures in solution were investigated by UV-visible spectrophotometry and 13C and 1H NMR spectrosccopy. Compound 4 crystallizes in the monoclinic space group P21/n with one independent molecule per asymmetric unit and 3 crystallizes in triclinic P-1 with three independent molecules per asymmetric unit. Rotation of the o-nitro group and of the amino group out of the aromatic plane was observed in both the solid state and in solution for both compounds. Copyright © 1998 John Wiley & Sons, Ltd.
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  • 134
    ISSN: 0894-3230
    Keywords: cryptand ; fluorescence titration ; lanthanide coordination ; proton transfer ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Lanthanide [lanthanum(III), 2; europium(III), 3; and gadolinium(III), 4] cryptates of a tris-phenylphenol N8O3 Schiff-base cryptand (H3L) were synthesized by transmetallation with [Na(H3L)]ClO4·3H2O (1) and characterized by spectroscopic and crystal structure analyses. Both 3 and 4 are isomophous and isostructural. The complexes crystallize in the triclinic space group P-1 with cell parameters for 3 of a = 14.9833(2), b = 15.42670(10), c = 16.3770(3) Å, α = 75.3760(10), β = 68.2640(10), γ = 77.0540(10)° and Z = 2 and for 4 of a = 14.9976(3), b = 15.4417(3), c = 16.35350(10) Å, α = 75.4980(10), β = 68.3180(10), γ = 76.8790(10)° and Z = 2. The structures reveal that one lanthanide ion is unsymmetrically encapsulated in the cryptand cavity with a second ligand (solvent DMF). Solution NMR and solid structural studies demonstrated that there are intracavity and intermolecular proton transfer processes during lanthanide complexation towards the cryptand. A fluorimetric titration in acetonitrile for Eu(III) ion to 1 afforded a novel fluorescence intensity (IF)-equivalents of Eu(III) ion (x) plot signaling a quenching (0 〈 x 〈 0.2)-enhancement (0.2 〈 x 〈 1) change with formation of the kinetically stable 1:1 cryptate. An energy-transfer mechanism is discussed. Copyright © 1998 John Wiley & Sons, Ltd.
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  • 135
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    Journal of Physical Organic Chemistry 11 (1998), S. 857-870 
    ISSN: 0894-3230
    Keywords: Yukawa-Tsuno equation ; substituent effect ; α-hydroxybenzylic cation ; benzoyl compound ; ab initio calculation ; basicity ; proton affinity ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Structures of α-hydroxybenzylic cations and their conjugate bases, which cover a wide variation of stability, were optimized by means of ab initio molecular orbital method at the RHF/6-31G* level. Total energies were calculated at the MP2/6-31G*//RHF/6-31G* + ZPE (scaled 0.9) level. Calculated relative proton affinities of the respective neutral molecules (benzoyl compounds; conjugate bases of α-hydroxybenzylic cations) agreed well with the corresponding basicities in the gas phase. The geometries of α-amino-α-hydroxybenzyl and α-hydroxy-α-dimethylaminobenzyl cations were also optimized at the fixed dihedral angles between the cationic 2pπ orbital and the benzene π orbital (φ), and between the cationic 2pπ orbital and lone pair electron orbital of the α-substituent (θ). The changes in Wiberg bond orders and the rotational potentials about φ and θ showed that the degree of resonance interaction between the cationic center and phenyl ring is balanced by the electronic effects of α-substituents in benzylic cations. The obtained theoretical indices of all parent cations such as Mulliken population, Wiberg bond order and bond lengths were correlated linearly with the resonance demand parameter (r value) which were given by the Yukawa-Tsuno substituent effect analysis in the gas phase and in aqueous solution. These relationships are consistent with those for other benzylic cations such as destabilized carbocations and sterically hindered cations studied previously. This confirms that the empirical r value has a definitive physical meaning, i.e. a measure of the resonance interaction between the cationic center and the aryl moiety. Copyright © 1998 John Wiley & Sons, Ltd.
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  • 136
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    Journal of Physical Organic Chemistry 11 (1998), S. 1-9 
    ISSN: 0894-3230
    Keywords: benzothiazole-2-thiol ; formation mechanism ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The formation of benzothiazole-2-thiol from aniline, carbon disulphide and sulphur at 230°C was shown to occur by a sequence of three principal steps. Labelling experiments confirmed that both sulphur atoms originate from carbon disulphide. An initial polar reaction to form thiocarbanilide via phenylcarbamic acid and a tetrahedral intermediate is followed by radical cyclization of these to benzothiazole-2-thiol and 2-phenylaminobenzothiazole; the latter is converted into the desired product by a polar displacement of aniline by H2S. Mechanisms for the formation of minor byproducts are also considered. © 1998 John Wiley & Sons, Ltd.
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  • 137
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    Journal of Physical Organic Chemistry 11 (1998), S. 223-229 
    ISSN: 0894-3230
    Keywords: Solvolysis ; Grunwald-Winstein-type analysis ; Hammett-type analysis ; YxBnCl scale ; 1-aryl-1-phenylmethyl cations ; Mulliken population analysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rate constants of solvolysis of α-tert-butyl(2-naphthyl)methyl chloride (1), 9-fluorenyl chloride (2) and a series of monosubstituted benzhydryl chlorides (3) in a wide range of solvents were measured. Grunwald-Winstein-type correlation analysis of log k for 2 and 3 against YBnCl, with or without nucleophilicity N, yielded less satisfactory linear correlations than that against log k(1). A new scale of solvent ionizing power, YxBnCl, for the correlation of solvolytic reactivities of benzylic chlorides with extended charge delocalization based on log k(1) was developed. Application to the mechanistic study suggested the solvolysis of 2 and 4-nitrobenzhydryl chloride were non-limiting. Hammett plots against σ+ constants exhibited more negative ρ values in less nucleophilic solvents. In a benzhydryl chloride containing a strong deactivating substituent, such as 4-nitro, the positive charge delocalizes mainly over the unsubstituted ring in the cationic transition state. The uneven charge distribution was also confirmed by Mulliken population analysis at the level of the RHF/6-31G*//RHF/3-21G(*) basis set for cations. Comparison of the results of correlation analysis using the equation log(k/k0) = mY vs the equation log(k/k0) = mY+hI, and using the equation log(k/k0) = mY+lN vs the equation log(k/k0) = mY+lN+hI indicated the use of YBnCl or YxBnCl could give a better understanding of solvolytic mechanisms than the combinatorial use of YCl and I. © 1998 John Wiley & Sons, Ltd.
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  • 138
    ISSN: 0894-3230
    Keywords: Solvent-solute interactions ; β-carotene ; electronic absorption spectrum ; solvent effects ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvent effects on the wavenumber of the maximum of the longest wavelength electronic absorption band of all-trans-β-carotene were determined in 34 solvents. Together with results from previous studies, a data set for 51 solvents, mostly non-hydrogen bond donors, was constructed. This information was analyzed in terms of reaction field models and also showed its value for correlation purposes when used either alone or in combination with standard empirical solvent polarity-polarizability scales. © 1998 John Wiley & Sons, Ltd.
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  • 139
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    Journal of Physical Organic Chemistry 11 (1998), S. 177-184 
    ISSN: 0894-3230
    Keywords: nitro derivatives of phenols ; pyrolysis initiation reactions ; impact sensitivity ; UHF-SCF-AM1 MO method ; activation energy. ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The UHF-SCF-AM1 MO method was applied to the study of two kinds of pyrolysis reactions of six nitro derivatives of phenols (homolysis reaction by rupture of the C - NO2 bond into radicals and isomerization reaction involving phenolic hydrogen transferring to oxygen on the NO2 group). The molecular geometries of reactants, transition states and products were fully optimized. The potential energy curves and activation energies were first obtained. The results show that this category of compounds is more easily initiated via isomerization reactions than by homolysis reactions. The parallel relationship among the Wiberg bond order of the pyrolysis-initiation H - O bond in the molecule of a reactant, the activation energy of the isomerization reaction breaking the H - O bond and impact sensitivity of the reactant gives ‘the principle of the smallest bond order’ (PSBO) powerful support. The sensitizing effect of a phenol group was elucidated based on calculation results. The different influences of OH and NO2 groups on the heat of formation of a molecule are discussed. © 1998 John Wiley & Sons, Ltd.
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  • 140
    ISSN: 0894-3230
    Keywords: 3-methyl-2, 4-diphenyl-3-azabicyclo[3.3.1]nonan-9α-ol esters ; analgesics ; synthesis ; structure ; conformation ; pharmacological assays ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of esters derived from 3-methyl-2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9α-ol (1) was synthesized and studied by 1H and 13C NMR spectroscopy, and the crystal structure of 3-methyl-2,4-diphenyl-9α-(3,5-dimethylbenzoyloxy)-3-azabicyclo[3.3.1]nonane (2) was determined by x-ray diffraction. The compounds studied display in CDCl3 a preferred flattened chair-chair conformation. This bicycle conformation is similar to that found for 2 in the crystal state. Pharmacological assays on mice were performed to evaluate drug-induced behavioral alteration, peripheral or central acute toxicity and analgesic activity. © 1998 John Wiley & Sons, Ltd.
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  • 141
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    Journal of Physical Organic Chemistry 11 (1998), S. 101-108 
    ISSN: 0894-3230
    Keywords: encounter complexes ; 1-cyanonaphthalene ; norbornadiene ; stereospecific ; nucleophilic trapping ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photo-induced electron donor-acceptor reactions between 1-cyanonaphthalene (CNN) and norbornadiene (N) generate products of several structure types. Methanol adducts (1-3) formed in polar solvents are rationalized via the radical cation, N+·, and stereospecific (exo-) nucleophilic attack by methanol. In less polar solvents, CNN and N form [2 + 2]-cycloadducts, exclusively on the exo-face of N. In non-polar solvents containing methanol, CNN, N and methanol combine to form 1:1:1 adducts, containing the sensitizer on the endo- and the methoxy groups on the exo-face. The formation of these products is rationalized via the trapping of encounter complexes of different geometries. Any rearrangement of the norbornenyl system can be eliminated, since neither tricyclyl nor 7-methoxynorbornenyl structures are formed. Apparently, the alcohol captures an endo-encounter complex of CNN and N by attack from the exo-face, similar to the attack of methanol on N+·. © 1998 John Wiley & Sons, Ltd.
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  • 142
    ISSN: 0894-3230
    Keywords: aromaticity ; Diels-Alder transition states ; Diels-Alder adducts ; reaction mechanism ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Semiempirical, ab initio and DFT investigations on the mechanism of the Diels-Alder reactions of a set of masked dienes (ring-fused dienes), viz. o-quinodimethane, anthracene and α-vinylnaphthalene, with ethylene, and reactions of α-vinylnaphthalene with maleic anhydride and p-benzoquinone were performed with a view to understanding the role of masking factors on the activation and reaction energies. The reactions were found to occur in a concerted fashion through synchronous transition states (TSs) in the first two reactions and through asynchronous TS in the other case. Of the compounds studied, o-quinodimethane is the most reactive diene both in a kinetic and a thermodynamic sense. α-Vinylnaphthalene reacts faster with maleic anhydride than p-benzoquinone, as expected, and two possible stereoselective TSs, one endo and the other exo, have been located for the reactions of α-vinylnaphthalene with the above dienophiles. Calculations show that the relative gain or loss of aromatic stabilization of the benzonoid ring in the transition state and in the product seems to play a major role in the kinetic and thermodynamic control of these reactions. © 1998 John Wiley & Sons, Ltd.
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  • 143
    ISSN: 0894-3230
    Keywords: methylbenzoic acids ; infrared spectra ; conformation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Infrared spectra of all isomers of polymethyl-substituted benzoic acids were recorded in the carbonyl and hydroxyl regions in tetrachloromethane at various concentrations and interpreted in terms of conformation. According to a plot of ν(C=O) of the monomeric form vs Hammett substituent constants σ, these compounds may be classified into two classes. Derivatives with none or only one methyl group in the ortho position are concluded to exist in an equilibrium of two planar conformations, unless the equilibrium is degenerate. Derivatives with two ortho-situated methyl groups are concluded to take up one non-planar conformation. These findings are supported by the shape of the hydroxyl and carbonyl bands, which are unsymmetrical in the former class, although they could not be reliably separated into bands pertinent to the individual conformers. This conclusion is at variance with the common interpretation which has invariably ascribed to these and similar ortho derivatives non-planar conformations with a variable torsional angle. © 1998 John Wiley & Sons, Ltd.
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  • 144
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    Journal of Physical Organic Chemistry 11 (1998), S. 15-24 
    ISSN: 0894-3230
    Keywords: electrophilic reactions ; electron transfer reactions ; electron-rich alkenes ; tetracyanoethylene ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Both experimental and theoretical studies confirm that the formation of aryl vinyl ether and aryl vinyl sulfide cation radicals from the corresponding neutral substrates correlates with the Brown σ+ parameters as opposed to Hammett σ values. Peak oxidation potentials for both classes of substrates correlate preferentially with σ+, as do gas-phase ionization energies calculated by both semi-empirical and ab initio methods. In contrast, the protonation energies of the same substrates, which relate to carbocation formation, correlate preferentially with σ values, as do rates of protonation and other electrophilic additions. These observations permit a sharp distinction between electrophilic and electron transfer reactions of these two common classes of electron-rich substrates. Using this criterion, the cycloadditions of tetracyanoethylene to these substrates are found to proceed via an electrophilic mechanism, rather than by a previously proposed electron transfer mechanism. © 1998 John Wiley & Sons, Ltd.
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  • 145
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    Journal of Physical Organic Chemistry 11 (1998), S. 25-30 
    ISSN: 0894-3230
    Keywords: 1,ω-bis(2-bromopyridinium)alkanes ; hydroxide ion ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reaction of OH- ion with 1,ω-bis(2-bromopyridinium)alkanes, where the reaction centers are separated by a varying number of methylene groups, was investigated to model the increased velocity of OH- attack on premicellar aggregated N-alkylpyridinium compounds. 1,ω-Bis(2-bromopyridinium)alkanes (RPBr) [R  =  propane (I), butane (II), pentane (III), hexane (IV) and octane (V)] were synthesized and characterized by standard procedures. The kinetics of I-V with OH- ion fitted two consecutive first-order reactions. The intermediate products, 1-(2-pyridone)-ω-(2-bromopyridinium)alkane, and also the final products 1,ω-bis(2-pyridone)alkanes, were isolated. Deuterium isotope effects, activation parameters and salt effects on the reaction rates suggest that OH- attack is rate limiting and there is a through-space acceleration of the initial attack due to the proximity of the positive charges. These results place an upper limit of 20-fold for the electrostatic acceleration in OH- attack in premicellar aggregates. © 1998 John Wiley & Sons, Ltd.
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  • 146
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    Journal of Physical Organic Chemistry 11 (1998), S. 47-53 
    ISSN: 0894-3230
    Keywords: N,N′-dicyclohexyl-O-(1-methylheptyl)isourea ; OH-acidic compounds ; acetic acid ; kinetics ; mechanisms ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Kinetic investigations on the reaction of N,N′-dicyclohexyl-O-(1-methylheptyl)isourea with acetic acid are described. The conversion proceeds partly through the intermediacy of a methylheptylcarbenium ion. However, in dilute solution an SN2 mechanism prevails. The results are discussed in terms of the simultaneous existence of two discrete mechanisms. © 1998 John Wiley & Sons, Ltd.
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  • 147
    ISSN: 0894-3230
    Keywords: calixarenes ; complexes ; conformation ; crystal structure ; 1H NMR ; 13C NMR ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal structure of 25,27-dihydroxy-26,28-bis(diethoxyphosphoryloxy)-tert-butylcalix[4]arene (1) (hexane solvate, 1:1) was determined by x-ray crystallography. The crystal data are P21/n, a  =  12.652(1) Å, b  =  12.564(2) Å, c  =  18.781(4) Å, β  =  105.56(1)°, V  =  2876.0(8) Å3, Z  =  2. In this complex the molecule adopts a 1,2-alternate conformation. Both the calixarene and hexane molecules are centrosymmetric. The phenol units in the asymmetric part of the calix are inclined with respect to the main macrocyclic plane by 115.46(6)° and 128.01(7)° for the phosphorylated and the non-phosphorylated ring, respectively. Self-inclusion of the ethyl chains in the half-cavities is observed. One intramolecular O - H…O and several intermolecular C - H…O hydrogen bonds are present. In the 1H NMR spectrum one average AX spin system for methylene bridge protons can be interpreted as fast (on the NMR time-scale) interconversion of non-phosphorylated phenol fragments. © 1998 John Wiley & Sons, Ltd.
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  • 148
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    Journal of Physical Organic Chemistry 11 (1998), S. 31-35 
    ISSN: 0894-3230
    Keywords: allyl alcohol ; oxidation ; alkaline periodate ; palladium(II) catalyst ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The oxidation of allyl alcohol by alkaline species of periodate, H2IO63-, was found to be catalysed by micro amounts of Pd(II) in 0.2 mol dm-3 alkali solution. The active species of the catalyst was found to be PdCl+. A mechanism involving the interaction of the catalyst and substrate in prior equilibria leading to the formation of a π-complex is proposed and the rate is derived. © 1998 John Wiley & Sons, Ltd.
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  • 149
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    Journal of Physical Organic Chemistry 11 (1998), S. 10-14 
    ISSN: 0894-3230
    Keywords: equilibrium acidities ; homolytic bond dissociation enthalpies ; benzaldoximes ; phenyl methyl ketoximes ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The equilibrium acidities in DMSO of nine p- and m-substituted benzaldoximes and eight p-substituted phenyl methyl ketoximes were measured. Estimates of the homolytic bond dissociation energies (BDEs) of the acidic O - H bonds in these compounds were made by combination of their pKHA values with the oxidation potentials of their conjugate bases, Eox(A-), using the equation BDE  =  1.37pKHA + 23.06Eox(A-) + 73.3 kcal (1 kcal  =  4.184 KJ). Plots of Eox(A-) vs pKHA for p-substituted benzaldoximes and p-substituted phenyl methyl ketoximes were linear with slopes near unity. Consequently, as required by the above equation, the BDEs estimated for the O - H bonds in these oximes were constant, being 88.3 ± 0.3 and 89.2 ± 0.4 kcal, respectively. © 1998 John Wiley & Sons, Ltd.
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  • 150
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 25-42 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: Considered is the rotation of a robot arm or rod in a horizontal plane about an axis through the arm's fixed end and driven by a motor whose torque is controlled. The model was derived and investigated computationally by Sakawa and co-authors in [7] for the case that the arm is described as a homogeneous Euler beam. The resulting equation of motion is a partial differential equation of the type of a wave equation which is linear with respect to the state, if the control is fixed, and non-linear with respect to the control.Considered is the problem of steering the beam, within a given time interval, from the position of rest for the angle zero into the position of rest under a certain given angle.At first we show that, for every L2-control, there is exactly one (weak) solution of the initial boundary value problem which describes the vibrating system without the end condition.Then we show that the problem of controllability is equivalent to a non-linear moment problem. This, however, is not exactly solvable. Therefore, an iteration method is developed which leads to an approximate solution of sufficient accuracy in two steps. This method is numerically implemented and demonstrated by an example. © 1998 by B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 151
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 59-91 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: A time-dependent Ginzburg-Landau-type model of a superconducting-normal-superconducting junction is presented. The existence and the uniqueness of the solutions are proved. When the data of the model are symmetric of some kinds, the solutions turns out to be symmetric of some kinds. In this symmetric case, an approximate model with the small thickness of the normal material in the middle of the junction as coefficients of a differential system is established for the sake of numerical computations. And also the existence and the uniqueness of the solution to this approximate model are set up. © 1998 by B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 152
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 165-185 
    ISSN: 0170-4214
    Keywords: boundary integral equations ; boundary finite element ; free edge polygonal plate ; hypersingular kernels ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider the problem of a polygonal plate with free edges. It is a boundary value problem for the biharmonic operator on a polygon with Neumann boundary conditions. Its resolution is studied via boundary integral equations. A variational formulation of the boundary problem obtained by a double-layer potential is given. Finally, we implement the method and give numerical results. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 153
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 227-249 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: Integral equations associated with the basic boundary value problems for the Laplace and Stokes equations are considered. The integral operators for these integral equations are interpreted as the pseudodifferential operators, and their principal symbols are calculated. The symbols are obtained in terms of the principal curvatures and the coefficients of the first quadratic form of the boundary. As a consequence, the initial approximation is suggested for the iterative methods solving the integral equations. © 1998 by B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 154
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 375-392 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In this work we analyse a model for radiative heat transfer in materials that are conductive, grey and semitransparent. Such materials are for example glass, silicon, water and several gases. The most important feature of the model is the non-local interaction due to exchange of radiation. This, together with non-linearity arising from the well-known Stefan-Boltzmann law, makes the resulting heat equation non-monotone. By analysing the terms related to heat radiation we prove that the operator defining the problem is pseudomonotone. Hence, we can prove the existence of weak solution in the cases where coercivity can be obtained. In the general case, we prove the solvability of the system using the technique of sub and supersolutions. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 155
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 463-477 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider the time-harmonic Maxwell equations in the high-frequency case for a heterogeneous medium, i.e., a medium which is composed by a conductor and a perfect insulator, or, in other words, a loaded cavity. As a consequence of a suitable compactness result, we prove that Fredholm alternative holds for such a problem. Since the kernels of the considered operator and of its adjoint are proven to be trivial, a unique solution exists for each given datum. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 501-517 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In this paper an initial-boundary-value problem in one-space dimension is studied for the Broadwell model extended to a gas mixture undergoing bimolecular reactions. Techniques of semigroup of bounded positive operators in a suitable Banach space are used to prove existence and uniqueness of the solution on bounded time intervals whose length depends on the initial data. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 589-603 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In the paper we study the problem of control by means of a heat source g for a thermoelastic system of equationsutt - ρ∇·p(θ, ∇u) - νΔut + DΔ2 u = f, cv(θ, ∇u)θt - κΔθ - ρθ[pθ (θ, ∇u)·∇ut] - ν∣∇ut∣2 = g, in a two-dimensional domain, where both viscosity ν and rigidity D are positive. Such a system has been considered in our former papers, and existence of solutions as well as uniqueness have been obtained. Here we prove the continuity and differentiability of solutions under somewhat stronger assumptions. An example of a control problem and necessary optimality conditions are presented. The system has an interpretation as a plate reinforced with shape memory alloy (SMA) wire mesh. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 619-651 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider acoustic scattering from an obstacle inside an inhomogeneous structure. We prove in the paper that if the outside inhomogeneity is known then the obstacle and possible inside inhomogeneity are uniquely determined by the fixed energy far field data. The proof is based on new mapping properties of layer potentials in spaces that specify one point. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 685-700 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In the present work, the problem of electromagnetic wave propagation in three-dimensional stratified media is studied. The method of decoupling the electric and magnetic fields is implemented, and the spectral approach is adopted, componentwise, to the vector equation involving the electric field. Operational calculus of self-adjoint, positive operators in suitable Hilbert spaces is used to solve the corresponding initial value problems. The spectral families of these operators for the cases of the whole space and of a finite layer are constructed. A discussion on the applicability of the obtained results to physical problems is also included. © 1998 B.G. Teubner Stuttgart-John Wiley & Sons Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 757-780 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In this paper we prove under the assumption of small initial data the global existence of a classical solution to the equations in viscoelasticity, associated with a free damping boundary condition. We also show that if we choose the initial data large enough, blow up will occur in finite time. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1115-1148 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We apply the Child-Langmuir asymptotics of the Vlasov-Poisson system to the case of a bipolar diode, i.e. a vacuum diode where two species of particles of opposite electric charge are flowing. This leads to a simplified model which, if at least one of the two injected currents is not too large, has a unique solution. Moreover, in that case, the currents flowing inside the diode are limited by the so-called bipolar Child-Langmuir currents. In the case of large currents, other solutions may appear, and the formation of virtual electrodes may occur inside the diode. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1149-1183 
    ISSN: 0170-4214
    Keywords: free boundary fluid motion ; Cauchy problem ; Hamilton structure ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: The Cauchy problem for the motion of a liquid drop under surface tension is solved locally in time on the basis of a general abstract existence theorem for Hamiltonian systems which seems to be of interest also in other areas. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 969-983 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We study the problem of the scattering by a periodic, inhomogeneous, penetrable medium. Using the Dirichlet-to-Neumann operator from the classical formulation of the problem we derive a variational equation and give regularity result to show the equivalence of both formulations. We present certain uniqueness results, which by the Fredholm alternative yield existence of the solution and its continuous dependence on the incoming wave. We prove existence of a solution for special incident waves even if there is no uniqueness. A result about analytical dependence of the solution on the wave number and the incident angle is given. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1185-1194 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In this paper we prove the global existence and study decay property of the solutions to the initial boundary value problem for the quasi-linear wave equation with a dissipative term without the smallness of the initial data. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1207-1226 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: Reaction random-walk systems are hyperbolic models to describe spatial motion (in one dimension) with finite speed and reactions of particles. Here we present two approaches which relate reaction random-walk equations with reaction diffusion equations. First, we consider the case of high particle speeds (parabolic limit). This leads to a singular perturbation analysis of a semilinear damped wave equation. A initial layer estimate is given. Secondly, we consider the case of a transcritical bifurcation. We use techniques similar to that of the Ginzburg-Landau method to find a modulation equation for the amplitude of the first unstable mode. It turns out that the modulation equation is Fisher's equation, hence near the bifurcation point travelling wave solutions are obtained. The approximation result and the corresponding estimate is given in terms of the bifurcation parameter. Both results are based on an a priori estimate for classical solutions which follows from explicit representations of the solution of the linear telegraph equation. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1365-1377 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In the article the problem of regulation of the cardiovascular system is investigated from the point of view of control process theory. This problem was reduced to finding the optimal control in the sense of speed in a bilinear system. In the first part of the article the possibility of applying Saburov's method for the solution to bilinear control problems is considered. The second part of the article is devoted to the application of this method to a concrete problem from practical medicine. The method has allowed the complete synthesis of an optimal control to be carried out  -  the sliding mode takes place and it was investigated completely. The results obtained are interesting from the point of view of control process theory, and testify to the high efficiency of the method. The final results allow concrete recommendations about the regulation of the cardiovascular system. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1399-1413 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: The steady-state equations for a charged gas or fluid consisting of several components, exposed to an electric field, are considered. These equations form a system of strongly coupled, quasilinear elliptic equations which in some situations can be derived from the Boltzmann equation. The model uses the duality between the thermodynamic fluxes and the thermodynamic forces. Physically motivated mixed Dirichlet-Neumann boundary conditions are prescribed. The existence of generalized solutions is proven. The key of the proof is a transformation of the problem by using the entropic variables, or electro-chemical potentials, which symmetrize the equations. The uniqueness of weak solutions is shown under the assumption that the boundary data are not far from the thermal equilibrium. A general uniqueness result cannot be expected for physical reasons. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 168
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1343-1363 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider an elastic plate with the non-deformed shape ΩΣ := Ω \ Σ, where Ω is a domain bounded by a smooth closed curve Γ and Σ ⊂ Ω is a curve with the end points {γ1, γ2}. If the force g is given on the part ΓN of Γ, the displacement u is fixed on ΓD := Γ \ ΓN and the body force f is given in Ω, then the displacement vector u(x) = (u1(x), u2(x)) has unbounded derivatives (stress singularities) near γk, k = 1, 2   u(x) = ∑2k, l=1 Kl(γk)r1/2kSCkl(θk) + uR(x)     near γk.Here (rk, θk) denote local curvilinear polar co-ordinates near γk, k = 1, 2, SCkl (θk) are smooth functions defined on [-π, π] and uR(x) ∊ {H2(near γk)}2. The constants Kl(γk),   l = 1, 2, which are called the stress intensity factors at γk (abbr. SIFs), are important parameters in fracture mechanics. We notice that the stress intensity factors Kl(γk) (l = 1, 2;  k = 1, 2) are functionals Kl(γk) = Kl(γk; L, Ω, Σ) depending on the load L, the shape of the plate Ω and the shape of the crack Σ. We say that the crack Σ is safe, if Kl(γk; Ω)2 + K2(γk; Ω)2 〈 RẼ. By a small change of Ω the shape Σ can change to a dangerous one, i.e. we have K1(γk; Ω)2 + K2(γk; Ω)2 ≥ RẼ. Therefore it is important to know how Kl(γk) depends on the shape of Ω.For this reason, we calculate the Gâteaux derivative of Kl(γk) under a class of domain perturbations which includes the approximation of domains by polygonal domains and the Hadamard's parametrization Γ(τ) := {x + τφ(x)n(x);  x ∊ Γ}, where φ is a function on Γ and n is the outward unit normal on Γ. The calculations are quite delicate because of the occurrence of additional stress singularities at the collision points {γ3, γ4} = ΓD ∩ ΓN.The result is derived by the combination of the weight function method and the Generalized J-integral technique (abbr. GJ-integral technique). The GJ-integrals have been proposed by the first author in order to express the variation of energy (energy release rate) by extension of a crack in a 3D-elastic body. This paper begins with the weak solution of the crack problem, the weight function representation of SIF's, GJ-integral technique and finish with the shape sensitivity analysis of SIF's. GJ-integral Jω(u; X) is the sum of the P-integral (line integral) Pω(u, X) and the R-integral (area integral) Rω(u, X). With the help of the GJ-integral technique we derive an R-integral expression for the shape derivative of the potential energy which is valid for all displacement fields u ∊ H1. Using the property that the GJ-integral vanishes for all regular fields u ∊ H2 we convert the R-integral expression for the shape derivative to a P-integral expression. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1495-1517 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: Inverse problems for identification of the four memory kernels in one-dimensional linear thermoviscoelasticity are reduced to a system of non-linear Volterra integral equations using Fourier's method for solving the direct problem. To this system of equations the contraction principle in weighted norms is applied. In this way global in time existence of a solution to the inverse problems is proved and stability estimates for it are derived. In analogous way inverse problems for the memory kernels in linear poroviscoelasticity can be handled. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1467-1477 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In this paper, the existence, both locally and globally in time, the uniqueness of solutions and the non-existence of global solutions to the initial boundary value problem of a generalized Modification of the Improved Boussinesq equation utt-uxx-uxxtt=σ(u)xx are studied and a few examples are discussed. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1619-1635 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider the two-parameter non-linear Sturm-Liouville problems. By using the variational method on general level sets, the variational eigenvalues are obtained. The purpose of this paper is to study the properties of these variational eigenvalues with respect to the parameter of general level sets. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 187-226 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We study the limit behaviour of solution of Poisson's equation in a class of thin two-dimensional domains, both simply connected or single-hollowed, as its thickness becomes very small. The method is based on a transformation of the original problem into another posed on a fixed domain, obtention of a priori estimates and convergence results when thickness parameter tends to zero. As an important application of abstract results we obtain the limit expressions for functions appearing in elastic beam theories as torsion and warping functions. In this way, we provide a mathematical justification and a correct definition of torsion, warping and Timoshenko functions and constants that should be used in the open and closed thin-walled elastic beam theories. © 1998 by B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 269-279 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: The generalized Möbius function and Möbius inversion formula are applied to a multiplicative semigroup. A general mathematical method based on this Möbius inversion is presented to solve inversion problems of expansions with unequally weighted terms. By this method, all the inverse lattice problems in physics can be solved concisely. The solutions of four inverse lattice problems: the Fibonacci structure, the square lattice structure, the bcc and the hcp lattice structures are given. These are difficult to be solved by other methods. © 1998 by B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 361-374 
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    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We use the eigenfunction expansion of Green's function of Dirichlet problems to obtain sampling theorems. The analytic properties of the sampled integral transforms as well as the uniform convergence of the sampling series are proved without any restrictions on the integral transforms. We obtain a one- and multi-dimensional versions of sampling theorems. In both cases the sampling series are written in terms of Lagrange-type interpolation expansions. Some examples and the truncation error as well as the stability of the obtained sampling expansions are discussed at the end of the paper. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 393-416 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider a dynamical von Kármán system in the presence of thermal effects. Our model includes the possibility of a rotational inertia term in the system. We show that the total energy of the solution of such system decays exponentially as t→+∞. The decay rates we obtain are uniform on bounded sets of the energy space. The main ingredients of our method of proof are suitable properties of a decoupled system, the energy method and the compactness of the nonlinear map associated to the von Kármán system. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 176
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 479-488 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: This short article discusses the spectrum of the Neumann Laplacian in the infinite domain Ω⊂∝n, n ≥2 created by inserting a compact obstacle P into the uniform cylinder Ω0 =(-∞, ∞)×Ω′. The main result is the existence of at least one embedded eigenvalue when P is an (n -2)-dimensional surface whose unit normal is parallel to Ω′ at each point of P . The special case when P is symmetric about {0}×Ω′ is also treated. It is shown that there is at least one symmetric eigenvector and, when P is sufficiently long, at least one antisymmetric eigenvector. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 551-564 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We prove the existence of solutions to the three-dimensional elastoplastic problem with Hencky's law and Neumann boundary conditions by elliptic regularization and the penalty method, both for the case of a smooth boundary and of an interior two dimensional crack. It is shown, in particular, that the variational solution satisfies all boundary conditions. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 178
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 565-588 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: New explicit stability conditions are derived for a linear integro-differential equation with periodic operator coefficients. The equation under consideration describes oscillations of thin-walled viscoelastic structural members driven by periodic loads. To develop stability conditions two approaches are combined. The first is based on the direct Lyapunov method of constructing stability functionals. It allows stability conditions to be derived for unbounded operator coefficients, but fails to correctly predict the critical loads for high-frequency excitations. The other approach is based on transforming the equation under consideration in such a way that an appropriate ‘differential’ part of the new equation would possess some reserve of stability. Stability conditions for the transformed equation are obtained by using a technique of integral estimates. This method provides acceptable estimates of the critical forces for periodic loads, but can be applied to equations with bounded coefficients only. Combining these two approaches, we derive explicit stability conditions which are close to the Floquet criterion when the integral term vanishes. These conditions are applied to the stability problem for a viscoelastic bar compressed by periodic forces. The effect of material and structural parameters on the critical load is studied numerically. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 179
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 653-664 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In order to maintain spectrally accurate solutions, the grids on which a non-linear physical problem is to be solved must also be obtained by spectrally accurate techniques. The purpose of this paper is to describe a pseudospectral computational method of solving integro-differential systems with quadratic performance index. The proposed method is based on the idea of relating grid points to the structure of orthogonal interpolating polynomials. The optimal control and the trajectory are approximated by the m th degree interpolating polynomial. This interpolating polynomial is spectrally constructed using Legendre-Gauss-Lobatto grid points as the collocation points, and Lagrange polynomials as trial functions. The integrals involved in the formulation of the problem are calculated by Gauss-Lobatto integration rule, thereby reducing the problem to a mathematical programming one to which existing well-developed algorithms may be applied. The method is easy to implement and yields very accurate results. An illustrative example is included to confirm the convergence of the pseudospectral Legendre method, and a comparison is made with an existing result in the literature. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 180
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 701-718 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: This article establishes the existence of a trapped-mode solution to a linearized water-wave problem. The fluid occupies a symmetric horizontal channel that is uniform everywhere apart from a confined region which either contains a thin vertical plate spanning the depth of the channel or has indentations in the channel walls; the forces of gravity and surface tension are operative. A trapped mode corresponds to an eigenvalue of the composition of an inverse differential operator and a Neumann-Dirichlet operator for an elliptic boundary-value problem in the fluid domain. The existence of such an eigenvalue is established by extending previous results dealing with the case when surface tension is absent. © 1998 B.G. Teubner Stuttgart-John Wiley & Sons, Ltd.
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  • 181
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 733-755 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In space-based robotics, one of the most important problems is the disturbance to the satellite attitude and to the satellite microgravity environment caused by satellite mounted robot operation. This paper reports on computer-aided motion planning strategies to overcome this problem. Point-to-point motion designs are generated which not only connect prescribed start and end points of the robot motion, but also simultaneously return the satellite to its original attitude. Theoretical characterizations of some of those motion designs are presented, as well as numerical results. The computation time required to produce such motion designs is 1 or 2 min on a workstation. Thus, it can be practical to use these motion plans in space. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 182
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 823-864 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Description / Table of Contents: On présente dans cet article un certain nombre de résultats concernant le potentiel vecteur associé à une fonction à divergence nulle dans un ouvert borné de dimension trois. En particulier, plusieurs types de conditions aux limites sont proposés, pour lesquels on discute l'existence, l'unicité et la régularité du potentiel vecteur. On analyse la convergence d'une discrétisation par éléments finis de ces potentiels et on indique une application concernant l'approximation de fluides visqueux incompressibles.© 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
    Notes: This paper presents several results concerning the vector potential which can be associated with a divergence-free function in a bounded three-dimensional domain. Different types of boundary conditions are given, for which the existence, uniqueness and regularity of the potential are studied. This is applied firstly to the finite element discretization of these potentials and secondly to a new formulation of incompressible viscous flow problems.
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  • 183
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1049-1066 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider particle transport in a three-dimensional convex region V, bounded by the regular surface ∂V. We assume that particles are specularly reflected by ∂V and that a source q is assigned on ∂V; more general non-homogeneous boundary conditions are also discussed. The problem is non-linear because the boundary condition is not homogeneous. We prove existence of a unique strict solution and by using the theory of semigroups we derive the explicit expression of such a solution in terms of the boundary source q. In the appendix, we indicate how some properties of affine operators can be used to derive the solution. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 184
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1085-1105 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: A phase-field model based on the Coleman-Gurtin heat flux law is considered. The resulting system of non-linear parabolic equations, associated with a set of initial and Neumann boundary conditions, is studied. Existence, uniqueness, and regularity results are proved. An asymptotic analysis is also carried out, in the case where the coefficient of the interfacial energy term tends to 0. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 185
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 797-821 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider the thermoelastic plate system,utt-γΔutt+Δ2u+αΔθ=0,θt-κΔθ-αΔut=0 and we make a comparison between the models in which γ=0 and γ〉0. We conclude that in the first case the plate system is of a parabolic type, while when γ〉0 the corresponding system has a hyperbolic behaviour. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 186
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 883-894 
    ISSN: 0170-4214
    Keywords: solitary wave ; stability ; long wave-short wave resonance equations ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: This paper concerns the orbital stability for solitary waves of the Long Wave-Short Wave resonance equations. Since the abstract results of Grillakis et al. [7, 8] cannot be applied directly, we can extend the abstract stability theory and use the detailed spectral analysis to obtain the stability of the solitary waves. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 187
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 985-1014 
    ISSN: 0170-4214
    Keywords: Vlasov-Poisson-Fokker-Planck ; long-time behaviour ; fundamental solutions ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We study the long-time behaviour of solutions of the Vlasov-Poisson-Fokker-Planck equation for initial data small enough and satisfying some suitable integrability conditions. Our analysis relies on the study of the linearized problems with bounded potentials decaying fast enough for large times. We obtain global bounds in time for the fundamental solutions of such problems and their derivatives. This allows to get sharp bounds for the decay of the difference between the solutions of the Vlasov-Poisson-Fokker-Planck equation and the solution of the free equation with the same initial data. Thanks to these bounds, we get an explicit form for the second term in the asymptotic expansion of the solutions for large times. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 188
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1015-1033 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We study stationary and quasistationary solutions of the relativistic Vlasov-Maxwell system of plasma physics which have a special form introduced (in the classical setting) by Rudykh et al. [9, 10]. The actual construction of such solutions leads to semi-linear elliptic equations. Under suitable assumptions on the ansatz functions, we are able to solve these equations by a sub- and supersolution approach. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 189
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1035-1048 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider an initial boundary value problem for a non-linear differential system consisting of one equation of parabolic type coupled with a n × n semi-linear hyperbolic system of first order. This system of equations describes the compressible miscible displacement of n + 1 chemical species in a porous medium, in the absence of diffusion and dispersion. We assume the viscosity of the fluid mixture to be constant. We prove, in three space dimensions, the existence of a global weak solution with non-smooth initial data for the concentration. The proof is based on the artificial viscosity method together with a compensated compactness argument. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 190
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1593-1617 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In this paper we study the following problem:ut-Δu=-f(u) in Ω×(0, T)≡QT,∂u ∂n=g(u) on ∂Ω×(0, T)≡ST,u(x, 0)=u0(x) in Ω, where Ω⊂∝N is a smooth bounded domain, f and g are smooth functions which are positive when the argument is positive, and u0(x)〉0 satisfies some smooth and compatibility conditions to guarantee the classical solution u(x, t) exists. We first obtain some existence and non-existence results for the corresponding elliptic problems. Then, we establish certain conditions for a finite time blow-up and global boundedness of the solutions of the time-dependent problem. Further, we analyse systems with same kind of boundary conditions and find some blow-up results. In the last section, we study the corresponding elliptic problems in one-dimensional domain. Our main method is the comparison principle and the construction of special forms of upper-lower solutions using related equations. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1681-1704 
    ISSN: 0170-4214
    Keywords: stratified medium ; acoustic waves ; self-adjoint operators ; spectrum ; limiting absorption principle ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider the acoustic propagator A=-∇·c2∇ in the strip Ω={(x, z)∊∝2∣0〈z〈H} with finite width H〉0. The celerity c depends for large ∣x∣ only on the variable z and describes the stratification of Ω: it is assumed to be in L∞(Ω), bounded from below by cmin〉0, such that there exists M〉0 with c(x, z)=c1(z) if x〈 -M and c(x, z)=c2(z) if x〉M. We look at the propagator A as a ‘perturbation’ of the free propagators Aj in Ω associated to the velocities cj, j=1, 2, and implement a ‘perturbative’ method, adapting ideas of Majda and Vainberg. The spectrum of A is defined in section 2, a limiting absorption principle is proved in section 3 outside of a countable set Γ(A). The points of Γ(A) can only accumulate at the left of the thresholds of the free propagators. The needed material about Aj, j=1, 2, and some technical estimates for A are given in Appendix. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 117-128 
    ISSN: 0170-4214
    Keywords: third-grade fluid ; existence ; uniqueness ; classical solution ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: The global existence and uniqueness of classical solution of steady motions of a third-grade fluid provided assumptions on positivness of μ (coefficient of viscosity) and α1, γ (material coefficients) is proved. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 129-163 
    ISSN: 0170-4214
    Keywords: wavelets on closed surfaces ; Dirichlet's and Neumann's problem ; scaling function ; scale discrete wavelets ; integral formulas ; exact fully discrete wavelet transform ; band-limited harmonic wavelets ; Runge-Walsh approximation ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: Wavelets on closed surfaces in Euclidean space ∝3 are introduced starting from a scale discrete wavelet transform for potentials harmonic down to a spherical boundary. Essential tools for approximation are integration formulas relating an integral over the sphere to suitable linear combinations of function values (resp. normal derivatives) on the closed surface under consideration. A scale discrete version of multiresolution is described for potential functions harmonic outside the closed surface and regular at infinity. Furthermore, an exact fully discrete wavelet approximation is developed in case of band-limited wavelets. Finally, the role of wavelets is discussed in three problems, namely (i) the representation of a function on a closed surface from discretely given data, (ii) the (discrete) solution of the exterior Dirichlet problem, and (iii) the (discrete) solution of the exterior Neumann problem. © 1998 by B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 251-268 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: The propagation of Hölder regularity of the solutions to the 3D Euler equations is discussed. Our method is a special semi-linearization of the vorticity equation combined with the classical Schauder interior estimates. © 1998 by B.G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 195
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 281-325 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We present a bending model for a shallow arch, namely the type of curved rod where the curvature is of the order of the diameter of the cross section. The model is deduced in a rigorous mathematical way from classical tridimensional linear elasticity theory via asymptotic techniques, by taking the limit on a suitable re-scaled formulation of that problem as the diameter of the cross section tends to zero. This model is valid for general cases of applied forces and material, and it allows us to calculate displacements, axial stresses, bending moments and shear forces. The equations present a more general form than in the classical Bernoulli-Navier bending theory for straight slender rods, so that flexures and extensions are proved to be coupled in the most general case. © 1998 by B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 865-882 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We present an initial-boundary value problem of a quasilinear degenerate parabolic equation for the settling and consolidation of a flocculated suspension. The corresponding definition of generalized solutions is formulated. It is based on an entropy integral inequality in the sense of Kružkov. From this definition, jump and entropy conditions that have to be satisfied at discontinuities, and an entropy condition valid on one boundary of the computational domain are derived. The latter implies a set-valued reformulation of the original boundary condition. It is interpreted geometrically and characterized by the solution of an auxiliary hyperbolic Riemann problem. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 907-938 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: This work is devoted to prove the existence of weak solutions of the kinetic Vlasov-Poisson-Fokker-Planck system in bounded domains for attractive or repulsive forces. Absorbing and reflection-type boundary conditions are considered for the kinetic equation and zero values for the potential on the boundary. The existence of weak solutions is proved for bounded and integrable initial and boundary data with finite energy. The main difficulty of this problem is to obtain an existence theory for the linear equation. This fact is analysed using a variational technique and the theory of elliptic-parabolic equations of second order. The proof of existence for the initial-boundary value problems is carried out following a procedure of regularization and linearization of the problem. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1269-1286 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider homogeneous solutions of the Vlasov-Fokker-Planck equation in plasma theory proving that they reach the equilibrium with a time exponential rate in various norms. By Csiszar-Kullback inequality, strong L1-convergence is a consequence of the ‘sharp’ exponential decay of relative entropy and relative Fisher information. To prove exponential strong decay in Sobolev spaces Hk, k ≥ 0, we take into account the smoothing effect of the Fokker-Planck kernel. Finally, we prove that in a metric for probability distributions recently introduced in [9] and studied in [4, 14] the decay towards equilibrium is exponential at a rate depending on the number of moments bounded initially. Uniform bounds on the solution in various norms are then combined, by interpolation inequalities, with the convergence in this weak metric, to recover the optimal rate of decay in Sobolev spaces. © 1998 by B. G. Teubner Stuttgart-John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1297-1342 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: The aim of the paper is to provide the mathematical foundation of effective numerical algorithms for the optimal design of periodic binary gratings. Special attention is paid to reliable methods for the computation of diffraction efficiencies and of the gradients of certain functionals with respect to the parameters of the non-smooth grating profile. The methods are based on a generalized finite element discretization of strongly elliptic variational formulations of quasi-periodic transmission problems for the Helmholtz equation in a bounded domain coupled with boundary integral representations in the exterior. We prove uniqueness and existence results for quite general situations and analyse the convergence of the numerical solutions. Furthermore, explicit formulas for the partial derivatives of the reflection and transmission coefficients with respect to the parameters of a binary grating profile are derived. Finally, we briefly discuss the implementation of the generalized finite element method for solving direct and adjoint diffraction problems and present some numerical results. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1441-1465 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In this paper we consider the inverse backscattering problem for Maxwell's equations in a non-magnetic inhomogeneous medium, i.e. the magnetic permeability is a fixed constant. We show that the electric permittivity ε is uniquely determined by the trace of the backscattering kernel S(s, -θ, θ) for all s∊∝, θ∊S2 provided that it is a priori close to a constant. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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