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  • 1990-1994  (608)
  • 1925-1929
  • 1991  (608)
  • Atomic, Molecular and Optical Physics  (238)
  • Industrial Chemistry and Chemical Engineering  (212)
  • Biochemistry  (158)
Materialart
Erscheinungszeitraum
  • 1990-1994  (608)
  • 1925-1929
Jahr
Schlagwörter
  • 101
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 249-259 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We have used density functional theory in the local density approximation, as implemented in the DMol-double numerical plus polarization (DMol/DNP) procedure, to calculate optimized geometries for a group of molecules containing only first-row atoms. The results are in generally satisfactory agreement with experimentally determined structures. The DMol/DNP atomic and molecular energies are rather poor, when compared to high-level ab initio GAUSSIAN 1 values (which are taken as the standard), but the errors do show excellent linear correlations with the total energies. These relationships allow the DMol/DNP results to be corrected to a high degree of accuracy, so that they can then be used to obtain atomization and dissociation energies that compare well with measured values. It is shown that the errors in the DMol/DNP energies tend to increase as the number of electrons becomes larger and the number of nuclei smaller.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 102
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 225-234 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Algebrants are generalized matrix functions; they are multilinear forms of which the determinant, the permanent, and the immanant are special cases. A formal definition and fundamental properties of algebrants was given in paper I of this series. The present work develops algorithms for computation of those algebrants that arise in computational spin-free quantum chemistry for valence bond (VB) wave functions built on nonorthogonal orbitals. Namely, we exploit the left- and right-hand antisymmetry of N P N ˚A to develop algorithms that greatly reduce or eliminate the N! problem. The algorithms can be implemented in any computer language; our implementation in FORTRAN is available upon request. The savings effected by spin-free vs Slater determinant versions of VB theory are illustrated for 2, 3, …, 10 electrons.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 103
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 235-248 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: To understand the density-gradient expansion approximation for the exchange-correlation energy of density-functional theory from a fundamental viewpoint, we have performed an analysis of the corresponding expansion of the Fermi-coulomb hole charge distribution. The Fermi-Coulomb hole represents the correlations between electrons resulting from the Pauli exclusion principle and Coulomb's law. The analysis is performed in the exchange-only approximation by considering the expansion for the Fermi hole to terms of O(▽3) as applied to atoms. Our study shows that the expansions to O(▽), O(▽2), and O(▽3) all severely violate the constraint of positivity, becoming progressively worse with increasing orders of ▽. Further, the expansion to O(▽2) also severely violates the constraint of charge neutrality. (Terms of O(▽) and O(▽3) do not contribute to this constraint or to the exchange energy.) Thus the description of the physics of Pauli correlations in atoms as given by this approximation is highly unphysical. In spite of this, the exchange energy to O(▽2) is superior to the local density approximation because the expansion hole better approximates the exact Fermi hole in the interior of atoms from which arise the principal contributions to the energy. However, the improvement is not substantial, as the oscillations in the expansion Fermi hole occur within the atom itself. For asymptotic positions of the electron, the expansion holes to each order neither approximate the local density approximation nor the exact Fermi hole. Thus we understand why the expansion cannot lead to accurate highest occupied eigenvalues. The oscillations of the expansion Fermi hole also demonstrate why the Slater potential and electric field that result from these hole charge distributions are singular. On the other hand, we show that the expansion approximation is mathematically consistent in that the coefficient of the gradient correction term for screened Coulomb interaction to O(▽2) as obtained from the approximate Fermi hole is the same as that derived from linear response theory. We conclude with remarks on the Coulomb hole as obtained within this gradient expansion approximation scheme.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 104
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 261-268 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The functionals adopted in the present work are those of DePristo and Kress [Phys. Rev. A35, 438 (1987)] for the kinetic energy, of Cedillo et al. [Phys. Rev. A38, 1697 (1988)] for the exchange energy, and of Wilson and Levy [Phys. Rev. B41, 12930 (1990)] for the correlation energy. In addition to the kinetic-, exchange-, and correlation-energy functionals, the total-energy functional used in the present calculations contains also the functional describing the interaction of the electrons with the atomic nucleus, and the functional describing the classical or direct part of the interaction among the electrons. Using these functionals, a two-parameter and a three-parameter variational density-functional calculation of the total atomic binding energy of the Ne atom is carried out. The electron (number) density of the Ne atom is modeled by using hydrogenlike one-electron radial wavefunctions (with the 2s radial function orthogonalized to the 1s radial function) containing two/three variational parameters. It is found that the calculated correlation energies are in reasonable agreement with the correlation energy value obtained from the Wilson and Levy expression with a Hartree-Fock electron density.
    Zusätzliches Material: 5 Tab.
    Materialart: Digitale Medien
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  • 105
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 269-279 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The molecular and electronic structures of ADPO 1, a model thiapentalene 2, and [Xe2F3]+ have been calculated in the local-density functional (LDF) formalism with polarized double numerical basis sets. The molecules were calculated to have planar C2ν structures in agreement with experiment and in contrast to Hartree-Fock molecular-orbital calculations. The vibrational spectra of all species were calculated to show that the optimized structures are indeed minima. The calculated spectrum of [Xe2F3]+ is compared with the experimental one and excellent agreement is found. These results demonstrate that the LDF method can be applied to the prediction of molecular structures containing hypervalent bonds.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
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  • 106
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 299-309 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Molecular dynamics simulation of mixed quantum-classical systems, in situations where the quantal degrees of freedom undergo transitions among states, poses a number of challenging problems. Among the difficulties are bifurcation of trajectories that evolve into different quantum states and proper treatment of quantum coherence. In this article we outline the problems and contrast the ways in which they are addressed by current methods for nonadiabatic molecular dynamics. In the course of this comparison we present a new result, the relationship between the velocity adjustment in the “surface hopping” method and the “Pechukas force,” as well as some new reflections on an old result, oscillatory yields in ion-surface scattering.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 107
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 289-297 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A density-functional theory describing the superconducting state of matter is presented. The formalism leads to a set of single-particle equations that are structurally similar to the Bogoliubov-de Gennes equations but (in contrast to the latter) incorporate both normal and superconducting exchange-correlation effects. It is demonstrated via a rigorous decoupling scheme that these single-particle equations are equivalent to a set of normal Kohn-Sham equations, and a BCS-type gap equation to be solved self-consistently with the Kohn-Sham equations.
    Materialart: Digitale Medien
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  • 108
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 311-323 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Determining mechanisms of chemical reactions involves finding dynamical paths between desired (given) reactant and product states. We have developed a method that is based on recasting the principle of stationary action into a general and computationally tractable form that yields all dynamical paths connecting the initial and final configurations of the system. Thus the method has advantages over the traditional initial-value trajectory calculations for solving such boundary value problems. We give some examples of reaction paths for H(2S) + O2(3Σg-) ↔ OH(2II) + O(3P) on the ground state potential energy surfaces HO2(2A″).
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 109
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 281-288 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Electrostatic solvation energies of singly charged monoatomic ions may be predicted from the knowledge of an electrostatic potential buildup from a physically meaningful ionic radius. Since the asymptotic behavior of the electrostatic potential for cations and anions do not follow the same pattern, different methodologies are needed. The reaction field potential required for the calculation of Born's solvation energies of singly charged cations may be obtained from the simple Thomas-Fermi-Dirac theory, based on the condition that the electrostatic potential of the ground-state atomic ions do exactly equal the negative of their chemical potentials. For singly charged anions, electrostatic solvation energies may be directly obtained from Sen-Politzer electrostatic potentials. Numerical results are presented for two representative series of ions and compared with experimental data.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 110
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 325-333 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The electrophilic substitution in a series of 5-aminobenzofurans was investigated by all-valence electron AM1 molecular orbital calculations. Various molecular properties of the reactants, intermediates, and products were computed and compared with available experimental data. The results indicate that while calculated ground-state charge densities cannot be used to predict reactivity and orientations, the relative thermodynamic stabilities of the reaction intermediates (arenium ions, σ complexes) reflected by calculated heats of formation (ΔHƒ) accurately indicated the isomers resulting from the kinetically controlled substitutions. The relative stabilities of the reaction products could be used to predict reaction preferences for the thermodynamically controlled electrophilic substitutions. Positions 4 for both aniline and 5-aminobenzofurans were the most susceptible toward electrophilic attack. The calculated ΔHƒ of the reaction intermediates, in good agreement with the experimental data, were capable of distinguishing between slightly nonequivalent positions such as the ortho and ortho prime to a substituent. Calculated AM1 ΔHƒ may represent practical guides in the prediction of sites of electrophilic aromatic substitutions for molecules with complex structures.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 111
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 347-358 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We have performed ab initio (3-21 G) calculations on the weakly bound donor-acceptor complex between benzene and tetracyanoethylene (TCNE) as a function of various intermolecular motions. The resultant potential energy surface (PES) was then fit to the product of analytical functions. Classical dynamics was performed on this PES by solving Hamilton's equations using a fourth-order Runge Kutta differential equation solver. Time steps were of the order of 1.0 femtosecond and the system was allowed to evolve for 1,000,000 time steps. Fast Fourier analysis of the resulting trajectories indicate that the primary intermolecular vibrational frequencies are 118, 228, and 232 cm-1. These correspond to the motion of the intermolecular separation coordinate, and the two twisting coordinates. We also discuss other possible solutions, zero-point energies, etc.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 112
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 371-385 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Some of the fundamental theoretical concepts for molecules in homogeneous strong magnetic fields are discussed. First, we perform the pseudoseparation of the center of mass motion for neutral as well as charged systems. The resulting Hamiltonian allows us to investigate the problem of the Born-Oppenheimer adiabatic separation of electronic and nuclear motion in the presence of a magnetic field. In particular, we study the most important differences to the field-free case. Finally we discuss the symmetry groups for molecules in a magnetic field and investigate the possibilities and effects of the interaction of molecular electronic states through nuclear motion. Even for diatomic molecules severely enhanced nonadiabatic effects may occur in a magnetic field.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 113
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 335-345 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In this work we analyze the interrelations between potential energy changes and molecular shape changes along the reaction paths for a series of ring-opening reactions. The processes studied correspond to the opening of the four-member rings of 1,2-dioxete, 2H-oxete, 2H-thiete, and 1,2-dithiete, which recently have been given considerable attention in the literature. We describe the molecular shape in terms of a continuum of fused-sphere surfaces, which are characterized by using molecular topological methods. The four processes cover a range of reaction enthalpies from largely exothermic to almost thermoneutral. The similarity between the configurations found along the reaction path is assessed quantitatively in terms of parameters associated with the molecular shape and the path itself. We find a correlation between the value of the energy barriers (and reaction enthalpies) and the similarity parameters. The correlation is comparable to that found in the case of various other processes, such as torsional changes, collisions, and intramolecular atom displacements or shifts. The results are in line with the intuitive correlations expected from the Hammond postulate.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 114
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 359-370 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A general procedure to evaluate the rotational state population distributions of the nascent photofragments from the photodissociation of polyatomic molecules has been implemented with the use of the kinematic distribution function developed by Chen and Pei [Chem. Phys. Lett. 124, 365 (1986)]. Numerical evaluations of rotational state population distributions of diatomic photofragments from photodissociation of the general class of triatomic molecules are presented. The calculated rotational state population distributions are compared with the most recent experimental data on OH and SH photofragments to obtain the information on the kinematic aspects of the photodissociating H2O and H2S molecules.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 115
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 401-414 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The study of atoms and ions in unusual environments is an area of current interest. Examples of such environments are the Crab pulsar, where magnetic fields well in excess of 1012 G are encountered and plasmas, studied under intense laser irradiation, where “confined” atoms are subjected to electric fields corresponding to laser fluxes of 1018 W/m2. In this article, a unified theoretical approach is presented to treat atoms in such intense fields. The major theoretical tool employed is the Bloch or canonical density matrix. This is used first for treating magnetic fields, numerical examples of heavy atoms, and ions in intense fields being referred to specifically. Then the same theory is used for “confined” atoms in intense electric fields. Very brief reference is made to molecules in magnetic fiels, with the illustrative example of the simplest molecular ion H2+.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 116
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 415-429 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We employ a method for solving the time-dependent Schrödinger equation for an atom or molecule in an intense, pulsed-laser field to study multiphoton emission processes. Single-electron effective potentials have been developed that reduce the computational effort required for multielectron systems. Illustrative results for electron and photon emission rates from krypton at 532 nm in the intensity range (1-4) × 1013 W/cm2 are presented and compared to recent measurements.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 117
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 387-399 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We studied the influence of the additives of tetracyanoethylene (TCE) (radical-anion acceptor) and the variations in exciplex concentration on the magnitude of time-resolved magnetic field effect in a delayed excimer fluorescence in polar exciplex system pyrene-N,N-diethylaniline. The nonmonotonous dependence of the magnetic field effect on tetracyanoethylene concentratration was found. The magnitude of the magnetic field effect was brought close to the predicted maximum limit of about 300 ns by decreasing the exciplex concentration. We conclude that the yield of the triplets, resulting from intercombination transitions in a singlet exciplex, is rather small. The upper limit for the rate constant of these transitions has been determined to be less than 4.6 × 106 s-1.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 118
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 431-440 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An orbital polarization (Hund's second rule) correction to local spin density (LSD) theory is developed in both a spherical harmonic basis and in a crystal field basis, and applied to the electronic band structure of FeO, CoO, NiO, and La2CuO4, resulting in a substantial enhancement of the LSD insulating band gap for NiO, and the creation of insulating band gaps for FeO, CoO, and La2CuO4.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 119
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 441-450 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Variational calculations have been carried out on the ammonia molecule using two-dimensional potential energy functions. The two dimensions used are the inversion and symmetrical stretching coordinates. If the potential function includes a term to describe the interaction between these two coordinates, the results are as good as those obtained in other studies using a six-dimensional potential function. The barrier height for the new potential function is 1857.5 cm-1.
    Zusätzliches Material: 10 Tab.
    Materialart: Digitale Medien
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  • 120
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 451-459 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Ab initio molecular-orbital calculations were carried out on carbon monoselenide (CSe), its cation CSe+, and the selenoformyl cation HCSe+. Equilibrium- and transition-state geometries on the potential energy surfaces (PES) were located at the HF and MP2 levels using a valence double-ζ (d, p) basis set on H and C and the Huzinaga valence triple-ζ (d) basis set on selenium, respectively. The global minimum on the HCSe+ (PES) is the linear species 3 with the dissociation energy towards H and CSe+ of 151.5 kcal mol-1 (MP4//MP2 + ZPE level). While at the HF level the strongly bent isomer 4 is a local minimum structure lying 67.8 kcal mol-1 above 3 and separated from 3 by a small barrier of 6.2 kcal mol-1, MP2 geometry optimizations suggest that CSeH+ isomer is unstable.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 121
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 479-487 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The UV photoelectron spectra of 2-halogenofurans, together with 3-iodo and 2,5-diiodofurans, have been studied. The assignment of the lower energy region of the spectra was based on correlation of the ring π- and halogen levels in the related compounds, resolved vibrational structure, and in case of 2- and 2,5-diiodofurans by considering the relative intensities of their He I/He II spectra.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 122
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 461-478 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Ab initio Hartree-Fock band structure calculations are presented for the first time for lithium phosphide (Li3P) and lithium arsenide (Li3As) in the hexagonal P6/mmm crystal structure. Results are compared to those for lithium nitride (Li3N). The new calculations for Li3N agree with previous Hartree-Fock calculations, except for the valence band structure where results of previous pseudopotential calculations are confirmed. Geometry optimization for Li3P yields a lattice parameter a of 4.45 Å and a c value of 4.80 Å. These values differ markedly from experimental results reported to be 4.271 and 7.590 Å, respectively. A similar discrepancy is found for lithium arsenide: a = 4.60 Å and c = 4.96 Å have to be compared to the reported experimental values of 4.397 Å for a and 7.824 Å for c. Force constants are derived for in-plane and interplane vibrations. The band structures for Li3P and Li3As are found to be very similar to the one calculated for Li3N. Using Li3P as an example, it is shown how the band structure of the insulator can be derived from the band structures of the two metallic constitutent Li2P and Li monolayers. The metal-insulator transition occurs if the inter-plane distance falls below 4.25 Å. Contrary to expectations raised earlier, it is found that the 3d electrons in arsenic are strongly localized, evidenced by a very narrow d band width of 0.1 eV. They cannot be used to explain the difference in conductivity between the phosphide and the arsenide. A Mulliken population analysis gives charge distributions close to the ideal ionic structure (Li+)3X3-, X = N, P, and As. Overall it is found that hexagonal lithium phosphide and lithium arsenide arsenide are more similar to lithium nitride and less anisotropic than suggested previously. This discrepancy could be due to the use of polycrystalline samples in earlier experiments.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 123
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The electronic structure of the polyhedral carboranes 1,5-dicarba-closo-pentaborane(5) and 1,5-dicarba-closo-pentaborane(3) is studied using ab initio calculations, and compared to that of their hydrocarbon analogs bicyclo[1.1.1]pentane and [1.1.1]propellane, respectively. The high symmetry and common topology of the carborane-hydrocarbon structural analogs force similar bonding patterns, and the carboranes show a unique three-center, two-electron CBC bond not previously observed in these species. This three-center bond is formally analogous to the σ-bridged-π bond in the hydrocarbons, but its strength is low and its C—C bond long. Analysis of the bonding in these carboranes along with that in 1,3-diborabicyclo[1.1.1]pentane, another[1.1.1]propellane analog, shows that the strength of their three-center bonds is directly related to the nature of the bridging group, but is independent of the type of bridgehead atom. 1,3-Diboretene, the carborane analog of bicyclo[1.1.0]butane, is also found to exhibit a similar bonding pattern to its hydrocarbon analog and to possess a CBC bond.
    Zusätzliches Material: 13 Ill.
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  • 124
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 507-526 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Ab initio calculations of the molecular geometry and electronic structure properties (charges, dipole moment, polarizability, HOMO and LUMO energies) of acrylonitrile, CH2=CH—C≡N, cis- and trans-2-butenenitrile, CH3—CH=CH—C≡N, 3-butenenitrile, CH2=CH—CH2—C≡N, and 2-methyl-2-propenenitrile, CH2=C(CH3)—C≡N are obtained at the 3-21G level. Results on three anionic derivatives of these molecules obtained at the 3-21+G level are also reported. Properties of the molecules in their isolated states are considered as a preliminary basis to compare initial steps of bulk and surface polymerization of vinylic monomers by electrochemistry under cathodic polarization.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 125
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 527-544 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Elucidating, from a molecular point of view, the differences and similarities in the properties and reactivity of matter in the gaseous compared to the condensed state is a subject of considerable current interest. Although there are a number of promising approaches to this problem, one of the alternatives involves the use of clusters that enable detailed spectroscopy and reactivity investigations to be accomplished as a function of degree of solvation under well controlled conditions. New insight into a variety of phenomena of interest in liquids have been derived from recent studies in our laboratory. In particular, the findings have contributed to unraveling the reactions of ionized functional groups in organic molecules that are influenced by solvation effects, identifying the structure of protonated complexes among species of varying proton affinities, and quantifying the variations in spectroscopic properties of chromophores as influenced by solvation and aggregation. Various examples from the author's laboratory are discussed, including solvation-driven reactions as well as alcohol and acetone dehydration reactions, the influence of clustering on the reaction of OH- with CO2, structures of protonated species comprised of water, ammonia, and trimethylamine; also presented are the results of studies of the influence of solvation on the absorption of photons in the chromophore of tyrosine, namely phenol.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 126
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 557-568 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A study of the electronic structure and spectroscopy of models of C60 and C70 cage structures has been carried out using the intermediate neglect of differential overlap (INDO) model Hamiltonian. The geometry for these cages was obtained using gradient-driven methods, and at least in the case of C60, where information is available, is in good accord with the calculations of others. Using a small active space of only single excitations, both configuration interaction (CI) and random phase approximations (RPA) yield spectra in excellent agreement with that obtained from recent experiments. The oscillator strength of the band calculated at ∼47000 cm-1, however, dramatically diminishes as the active space is increased, even though the sum rule increases. We discuss this interesting observation as well as the calculated structure and spectrum of C70.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 127
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 545-555 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We examine the inclusion of spin-orbit effects within the Rumer configuration interaction technique and discuss its implementation in the spectroscopic version of the intermediate neglect of differential overlap model (INDO/S-CI). An efficient strategy for calculating excitation energies, transition moments, and Mulliken populations for Rumer-adapted functions is described. As an example, results are presented for the ground and excited states of the hydrated trivalent cerium ion [Ce(H2O)9]3+, which confirm the low energy assignments to 4ƒ → 5 d transitions split by some 10000 cm-1 through spin-orbit coupling and ligand field interaction. Comparisons are made between this technique and one that we have used previously that utilizes configuration interaction over double-group adapted linear combinations of determinants.
    Zusätzliches Material: 2 Ill.
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  • 128
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 569-576 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The angular and energy dependence of minima of the differential scattering cross section (DCS) for electrons scattered elastically by selected target atoms is studied using the nonrelativistic Hartree-Fock wavefunction for the static field and local energy-dependent function for the exchange and polarization potentials for the target atoms. The parameters contained in the polarization potential are varied to determine the minima of the DCS with respect to the scattering angle and incident energy with the constraint that the integral cross section agrees with the experimental value within the uncertainty of 5% at a selected energy. The resulting effective interaction potential is then used to compute the DCS over the intermediate energy range for the target atoms. The computed values are in good agreement with recently published experimental and theoretical cross section for helium and neon atoms.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 129
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 577-585 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Using computational SCF and MCSCF followed by extensive variational and perturbational CI calculations, we study the insertion routes of a copper atom into the carbon-hydrogen bond of a methane molecule. Here we show the importance of the initial reaction routes of the interaction for obtaining the final products of maximal probability. Because of the initial conditions of this reaction, our study shows that not all of the HCuCH3 intermediate complex dissociation channels in Part I can be easily reached. Another important result presented is the nonlinearity of the intermediate product HCuCH3. Finally, the results are discussed in light of low temperature matrix photoexcitation experiments and a comparison of this Cu—CH4 interaction with previous studies of the activation of the hydrogen molecule by copper is presented.
    Zusätzliches Material: 3 Ill.
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  • 130
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 587-591 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: From ab initio SCF-MO calculation using a 6 - 31G** basis set, the relationship between the topology of the charge distribution and the electric field gradient (EFG) at the nuclei of the two-coordinated N atoms was determined in imines with R = H2C =, HFC =, NCHC =, and H3CHC =; di-imides with R = H, F, and CN; and the monocyclic azines with one and two N atoms in it. It was found that the N nuclear quadrupole coupling constant was determined by the nonbonded concentration of N valence shell while the asymmetry parameter has contributions from this shell and also from the rest of the molecule.
    Zusätzliches Material: 1 Ill.
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  • 131
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 593-602 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The effects of solvent-solute interactions on polarized and depolarized Raman intensity are investigated using perturbation theory, accounting for correlations in the relative orientations of the interacting transition dipoles. Two mechanisms for intensity borrowing are considered: interaction of the vibrational transition moments in the ground electronic states, and coupling of the electronic transition moments responsible for resonance Raman enhancement. The first type of interaction is shown to lead to measurable frequency shifts and depolarization ratio changes for two coupled vibrations which are infrared active and close in frequency. The second mechanism, not dependent on vibrational resonance, leads to perturbations of the depolarization ratio in resonance Raman, but not to vibrational frequency shifts.
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  • 132
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 603-618 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The restricted Hartree-Fock formalism applied to quasi one-dimensional translational systems embodies slowly convergent Coulomb and exchange lattice summations. In this contribution, an algorithm based on a Filon like quadrature procedure to carry out the k-space integration of density matrix elements is analyzed and its efficiency is illustrated by its application to the linear chains of hydrogen molecules. It allows the computation of Coulomb and exchange lattice sums to their asymptotic limit, and renders obsolete the empirical procedure of guessing the number of interactions to be included in the calculations.
    Zusätzliches Material: 5 Ill.
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  • 133
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 619-628 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The hybrid method having features of ab-initio crystal orbital and ab-initio molecular cluster methods is proposed. In the approach presented the molecular crystal is treated as an infinite chain in a direction z, while two other directions are simulated by finite interactions of the molecular type. The new approach is especially useful for an investigation of anisotropic crystals. Test calculations for the carbon dioxide crystal are presented. The method was also employed for the investigation of a dissociation pathway of C—N bond in nitromethane in nitromethane crystal.
    Zusätzliches Material: 4 Ill.
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  • 134
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 629-639 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The linear combinations of Gaussian-type orbitals-fitting function (LCGTO-FF) technique has been used to calculate the binding energy and electronic band structure of a 3-atom-thick film extracted from bulk LiBeH3 in the cubic perovskite structure. The film is composed of an interior layer of LiH sandwiched between two exterior layers of BeH2, i.e., there are eight atoms per unit cell (1 Li, 2 Be, and 5 H). The calculated cubic lattice parameter for the 3-layer (a = 5.74 au) lies roughly midway between the previously published theoretical lattice parameters for a BeH2 monolayer (5.51 au) and bulk LiBeH3 in the cubic perovskite structure (5.89 au). The 3-layer film is predicted to be a semimetal (i.e., zero-gap semiconductor), unlike both bulk LiBeH3 which is predicted to be a semiconductor, and monolayer BeH2, which is predicted to be a good metal. The metallic nature of the 3-layer is due to a Be surface state that cuts across the other valence bands of the film, in good agreement with an earlier prediction that cubic perovskite LiBeH3 cleaved to expose a BeH2 layer would provide a metallic surface on an insulating substrate. The fact that the density of states goes to zero at the Fermi level is a direct result of the symmetries of the one-electron states.
    Zusätzliches Material: 5 Ill.
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  • 135
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 641-657 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A quantum mechanical time-dependent method was used to study the dynamics of dissociative adsorption and associative desorption of H2 on a flat, static surface. We used a two-dimensional model in which the molecular axis was held parallel to the surface and the diatom internuclear separation and distance above the surface were the dynamic variables. A modified London-Eyring-Polanyi-Sato (LEPS) potential described the molecule-surface interactions. The wave function for the molecule was represented by its values on a spatial grid of points. The wave function was propagated by expanding the time evolution operator in a series of Chebyshev polynomials and using the properties of the Fourier transform to calculate the kinetic energy. The computational requirements of the problem were significantly reduced by using an L-shaped grid which deletes a large number of points where it is known a priori that the wave-function amplitude vanishes. State-to-state transition probabilities were calculated as a function of the initial translational and vibrational energy for potentials with early, late, and intermediate barriers. The location of the barrier has a strong effect on the energy threshold for reaction and on the distribution of energy between vibration and translation in the products.
    Zusätzliches Material: 4 Ill.
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  • 136
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 659-669 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In this work we deal with ab initio and semiempirical calculations of single and multiple Al → Si replacements in the ZSM-5 structure. Substitutional energies for single replacements were obtained for cluster models of monomers, hexamers, and for the secondary building unit (SBU) of the zeolite by means of nonempirical SCF calculations, as well as the modified neglect of differential overlap (MNDO) method for extended clusters. The choice of the semiempirical methods for the study of multiple Si replacements by Al in the extended cluster model of the SBU is justified from the results with monomers and hexamers where the replacement energies obtained with MNDO are qualitatively the same as those from ab initio calculations. According to the results, a site occupancy order in the unit cell of the ZSM-5 network is derived from multiple Al → Si substitutions in the SBU, providing a theoretical basis for the Loewenstein-Dempsey Al sitting avoidance rules. Likewise, a Si/Al limit ratio in the Mobil FIve (MFI) zeolite, along with the corresponding Al distribution pattern in the unit cell, are also obtained.
    Zusätzliches Material: 6 Ill.
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  • 137
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 671-686 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Due to the mass effect, muonic molecular ions are about 200 times smaller than their electronic counterparts. The proximity of the nuclei in the tdμ ion results in fusion taking place within a picosecond. The properties of this ion are central to understanding the phenomenon of muon catalysis. We developed a computational method of solving the nonadiabatic Schrödinger equation for the bound and resonant states of tdμ and its isotopic analogues. The method takes into account both the Coulomb interactions and the strong nuclear forces responsible for the fusion reaction. The wave functions obtained from our method were used to predict very accurately branching ratios and transition rates relevant for various stages of the muon catalytic cycle. Knowledge of these quantities will guide the experiments and help to answer the question of feasibility of net energy production via muon catalysis.
    Zusätzliches Material: 3 Ill.
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  • 138
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 687-702 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: This article describes the computation of the tunnel current in a scanning tunneling microscope (STM). The calculation accounts for the three-dimensional scattering taking place simultaneously in the first atomic layers of the sample and in the apex of the probing tip. The model is built with the following ingredients: (a) the tip is represented by a cluster of atoms attached to an otherwise planar, free-electron metal surface, and (b) the analyzed sample is a planar free-electron metal with a local potential corrugation induced by an isolated molecule or adatom. The potential barrier includes the strong bending effect due to the image-charge formation occurring as the tunneling electron crosses the gap between the tip and the sample. The specific theoretical approach designed to solve this scattering problem exploits the fast Fourier transform algorithm to construct a transfer matrix in a mixed real- and momentum-spaces representation. The total current is obtained by summing the contributions of all scattered waves traveling in the barrier between the tip and the sample, and it is studied in this article for various positions of the tip relative to the adsorbed atomic cluster. The theory is used here to simulate the scan of a model-aluminum atom on a free-electron metal substrate using electrons focused by a single-atom tungsten tip.
    Zusätzliches Material: 8 Ill.
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  • 139
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 689-698 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Bonding in transition-metal molecules presents novel features: (i) s electron bonding is overcome by multiple d electron bonding, (ii) intraatomic exchange favoring atomic magnetization competes with bonding that tends to pair the electrons, and (iii) in the heteronuclear dimers, the ionic terms may be important due to strong charge-transfer effects. The NbIr heteronuclear diatomic molecule shows all these features clearly. The cellular multiple scattering-xαβ calculation presented in this paper shows the ground state to correspond to antiferromagnetic coupling between the highly magnetic Nb atom and the Ir atom. A one-electron charge transfer from Nb to Ir was found; the result is an ionic structure, Nb+Ir-, for the dimer. The computed equilibrium distance, 4.100 a.u., corresponds to a region where d bonding strongly overcomes the s bonding, which alone would have stabilized the molecule at 5.950 a.u. At intermediate interatomic separations, 5.35 a.u., the NbIr system has a state in which all molecular orbitals are bonding with a high hybridization between the ns and (n - 1)d electrons of each atom, resulting in a (almost entirely) covalent high multiple-bond formation for this meta-stable state of the dimer.
    Zusätzliches Material: 4 Ill.
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  • 140
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 747-754 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An orthogonalization procedure is presented that allows construction of at least (n-m) vectors orthogonal to {Xj}, j equals; 1, m, by linear combinations solely among {ηi}, i equals; 1, n, n〉m, and 〈Xj/ηi〉≠0. An important application of the procedure is in effective core potential methods for which valence orbitals can be constructed that are orthogonal to the core orbitals and yet involve no component of the core. Thus, a separate calculation for only the valence electrons can be performed without any explicit reference to the core electrons (orbitals).
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  • 141
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 225-242 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The Green-function method is a well-known way to reduce the quantum mechanical problem of n electrons moving in the field of clamped nuclei to the problem of solving a one-electron Schrödinger equation (the quasi-particle equation) involving a pseudopotential (the self-energy). This method is widely used in solid-state, low-energy electron-molecule scattering, ionization, and electron attachment theory, and much work has focused on finding accurate self-energy approximations. Unfortunately, the operator nature of the fundamental quantity (Green function) in the usual quasi-particle equation formalism significantly complicates the derivation of self-energy approximations, in turn significantly complicating applications to inelastic scattering and multiconfigurational bound-state problems. For these problems or wherever the operator approach becomes inconvenient, we propose an alternative quasi-particle equation derived wholely within a configuration interaction wave-function formalism and intended to describe the same phenomenology as does the Green function quasi-particle equation. Our derivation refers specifically to electron removal but is readily generalized to electron attachment and scattering. Although the Green function and wave-function quasi-particle equations are different, we emphasize the parallels by rederiving both equations within the equations-of-motion formalism and then producing a wave-function analog of the Green function two-particle-hole Tamm-Dancoff approximation.
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  • 142
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. ix 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 143
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 37-48 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The transfer of a proton from A to B in AH+‥B‥C to form A‥+HB‥C is expected to enhance the binding energy of C to the remainder of the H-bonded chain since C is now adjacent to a charged ion rather than to a neutral molecule. But since the actual proton motion between A and B is typically only 1 Å or so, the interaction should be considerably less than that in isolated +HB‥C. Ab initio calculations with a variety of basis sets are used to quantitatively measure the enhancement of this binding energy. Systems investigated include the homotrimers of water and of ammonia, ammonium-formate-water, and formic acid-imidazole-water.
    Zusätzliches Material: 2 Ill.
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  • 144
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 235-250 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 145
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 399-409 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The effects of perturber gases, partial pressures in the range 0-50 atm, on the absorption spectra of high-n Rydbergs, n ≥ 10, in methyl iodide and benzene have been investigated. The perturbers were rare gases and H2. It has been shown that the spectroscopic energy shift Δ = Δ(ρ, n) is given by Δ = Δ°ρ, where ρ is the number density of the perturber, for n ≥ 10. The shift data can be interpreted using a Fermi model, and values of scattering lengths for perturbers can be extracted. These scattering lengths are internally consistent, independent of the absorber, and in excellent agreement with electron-swarm results. Given that the Fermi model is nonspecific and microscopic, scattering shifts and lengths for mixtures of perturber gases can be predicted. These predictions, having been verified by experiment for He/Ar mixtures, provide a means of “tailoring” any required scattering length. Finally, it is shown empirically that the determinative scattering parameter is the polarizability of the perturber, and a universal relationship a = -0.26α + 1.18 between scattering length a, in Bohr radii, and polarizability α is found to exist.
    Zusätzliches Material: 9 Ill.
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  • 146
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 449-454 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The intermolecular modes of the bifurcated water dimer are determined at the HF level using an extended basis set. In these computations, the donor libration frequency is found to be real and the bifurcated structure does not collapse toward the linear dimer. This result is contrary to all previous ab initio computations, which have predicted a Hessian with one negative eigenvalue. A good representation of other intermolecular modes, such as the libration of the acceptor, also requires an extended basis set. An interesting infrared active transition is predicted around 444 cm-1. This transition, which corresponds to the donor wag, is found in the low-temperature spectrum of water in a N2 matrix.
    Zusätzliches Material: 2 Tab.
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  • 147
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991) 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 148
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 561-583 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Perturbation theory for the rate constant of nonadiabatic solvation is presented. Miller's treatment of the RRKM theory is used for the unperturbed rate constant, and thereby the “string model” of chemical reaction is used for the description of the perturbation of solvation. The reaction path under the influence of the external force field is defined as the intrinsic reaction coordinate (IRC) that is treated as a string. The string is thrown in the external static force field that acts as a nonadiabatic source of perturbation. As an application of the present treatment, the effect of the external point charge for hydration reaction of CO2 is calculated as a preliminary model for catalytic activity of the carbonic anhydrase in the tissues and lung capillary vessels.
    Zusätzliches Material: 15 Ill.
    Materialart: Digitale Medien
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  • 149
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 379-388 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We have recently proven an inequality for the exact noninteracting kinetic energy density functional \documentclass{article}\pagestyle{empty}\begin{document}$ T_s [n]:\mathop {\lim }\limits_{x \to \infty } T_s [n_\lambda ^x] \le T_s [n_s^y [n] + T_S^2 [n] 〈 \infty,where{\rm }n_\lambda ^x (x,{\rm }y,{\rm }z) = \lambda n(\lambda x,{\rm }\lambda {\rm y, }\lambda z) $\end{document}. It is known that the gradient expansion through fourth order, TsGE[n], violates this inequality. Toward improving TsGE[n], we have constructed two new functionals, Ts1[n] and Ts2[n], by keeping the zeroth and second orders in TsGE[n] and replacing the fourth order with two simple terms, respectively, so that these new functionals satisfy the inequality. Numerical tests are presented for Ts1[n], Ts2[n], and TsGE[n] and for the gradient expansion through second order. Hartree-Fock and hydrogenic atomic densities are employed.
    Zusätzliches Material: 2 Tab.
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  • 150
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 429-432 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 151
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991) 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 152
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 491-500 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Two possible reaction paths for the pyrolysis of the ethylester of glyoxylic acid have been studied by ab initio molecular orbital calculations. The basis sets 3-21G and 6-31G* have been used, and electron correlation has been included by Møller-Plesset calculations up to fourth order. Our calculations indicate that the reaction leading to acid and ethylene through a 6-membered ring transition state is favored relative to a process involving a formyl hydrogen transfer via a 5-membered ring to the alkyl unit leading to ethane, CO, and CO2. The predicted activation energies for these two reactions obtained at the highest level of calculation, MP4(SDTQ)/6-31G*, are 50.4 and 71.7 kcal/mol, respectively. The transition states have RHF wave functions that are stable relative to UHF solutions using the 3-21G basis. The geometry of the transition states and IRC following indicate that both reactions are strongly asynchronous: The C—O bond rupture is virtually completed before hydrogen transfer occurs. For comparative purposes, analogous calculations have been performed for the ethylester of formic acid, where it is confirmed that a 6-membered ring transition state is preferred relative to a 4-membered one by around 42 kcal/mol at the highest level of calculation.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 153
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 545-558 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A time-dependent molecular orbital method has been developed to study charge transfer in collisions of ions with metal surfaces at energies between 1 and 100 au. A set of localized basis functions consisting of generalized Wannier functions for the surface and s- and p-atomic functions for the ion, is used to separate the system into primary and secondary regions. An effective Hamiltonian and time-dependent equations for the electron density matrix are obtained in the primary region, where most charge transfer occurs. The equations for the electron density matrix are solved with a linearization scheme. The method is suitable to study atomic orbital orientation for collisions of ions and surfaces. A model calculation for Na+ + W(110) collisions with a prescribed trajectory is presented. The interaction potentials between the W(110) surface and Na+ 3s and 3p orbitals are calculated from Na+ pseudopotentials. Results show that the yield of neutralized atoms in 3p states changes as the collision energy is lowered.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 154
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 605-609 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: It is shown that the dispute about the conditions for physical admissibility of Schrödinger wave functions may be settled if the following two questions are clarified: (a) Are these condittions rooted in the foundations of quantum mechanics or invoked only for particular physical models? (b) Do we consider either the position-space wave function or the momentum-space wave function? Both the case of closed states and scattering states are considered. Some general remarks about these conditions are made in the Conclusion.
    Materialart: Digitale Medien
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  • 155
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: The variation in the behaviour of bulk solids as a result of sudden pressure changes in the surrounding gas phase is of interest in the application of lock hoppers for transfer of bulk solids into pressure vessels. By using such sluice systems, problems occur due to consolidation of the pressurized bulk solids. This paper presents the results of experimental and theoretical research, which allow to describe the influence of several parameters on pressure compensation and the degree of consolidation. With reference to the forces and mechanisms responsible for consolidation, it is possible to describe the different consolidation behaviour of incompressible (limestone) and compressible (hard coal) bulk solids.
    Zusätzliches Material: 12 Ill.
    Materialart: Digitale Medien
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  • 156
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 65-72 
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: A study was made of the flow characteristics of large oscillating drops of pure liquid-liquid systems, using a thermostatically-controlled, rising drop column, 50 mm in diameter and 1000 mm in length. Mirrors in the jacket enabled front and side views of drops to be photographed simultaneously. Single drops in the size range 5-10 mm were investigated with both mutually-saturated phases and when the solute was being transferred from the dispersed phase. The systems studied were (1) toluene and acetone (dispersed)-water (continuous), and (2) n-heptane and acetone (dispersed)-water (continuous). Acetone concentrations were varied up to 3.75 kmol/m3. The oscillations of a travelling drop were asymmetrical; therefore, the amplitude cannot be expressed accurately in terms of only two axes. The area change of the drop compared to that of a sphere of equal volume ‘ε’, was shown to represent the amplitude accurately. The periods of droplet oscillation were uniform for the mutually saturated systems of constant physical and flow properties but changed when mass transfer was taking place. The interfacial tension exerted a marked effect on the amplitude, which also depended upon the oscillation frequency. The amplitude changed with droplet size in a similar manner to the terminal velocity, i.e. it increased with increasing size until it reached a maximum, subsequently decreasing less rapidly. The drag coefficient increased with increasing rate of mass transfer from the drop. Correlation of the results and the area eccentricity ‘ε’ by dimensional analysis embracing all possible parameters and physical properties affecting drop oscillation, resulted in the correlation ε = 0.22 Sr0.42 We-0.53 M0.13 with a mean deviation of ± 14%. This will facilitate more accurate prediction of the interfacial area for mass transfer calculations, relating to equipment containing droplets in the oscillating regime.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 157
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 113-117 
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: The reduction of nitric oxide with ammonia on iron oxide catalysts has been studied in a continuous-flow recycle reactor using simulated flue gas in the temperature range from 573 to 673 K. NO and HN3 concentrations were varied between 0 and 1000 vpm, O2 and H2O concentrations between 0 and 9 vol.-%, the remainder being nitrogen. In the presence of oxygen, the formulated reaction rate equation describes the measured rates of the main reaction NO + 2/3 NH3 ⇄ 5/6 N2 + H2O. Its form corresponds to the Langmuir-Hinshelwood type. The rate equation well fits the data, which cover the whole industrial temperature and concentration range. In the absence of oxygen, the measured reaction rates can be best described by a power law.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 158
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: A new transport system has been developed which combines vibration of the conveying pipe with amplitudes of the order of fractions of a millimetre with rather low superficial velocities of the carrier gas. This new system was specially designed for gentle transport of fragile particulate materials.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 159
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 147-161 
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: In this study, we investigated the limits of safe operation for a cooled reactor, operated batchwise. As an example of a single-phase reaction, we studied the decomposition of t-butyl peroxypivalate, a well-known organic peroxide, undergoing self-heating at relatively low temperatures. If sufficiently diluted, it can be supplied to a polymerization process from large, cooled but unstirred vessels. We present a number of extensions to the existing homogeneous explosion theory, namely a practical definition of the critical condition, its calculation, and expressions for the available time before runaway in the case of a supercritical condition, taking into account the effects of natural convection inside the vessel and the reactant conversion. The extensions of the theory were confirmed by adiabatic and non-adiabatic runaway experiments on bench scale, and natural convection cooling experiments with liquids in various packages.
    Zusätzliches Material: 13 Ill.
    Materialart: Digitale Medien
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  • 160
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: This contribution deals with the consequences of the decrease in diffusion coefficients at the boundaries of miscibility in fluid systems and its effect on the mechanisms of mass transfer. The liquid-liquid (1-1) extraction involving several components is taken as an example for the discussion of this topic. A short review of Hampe's theory on transport mechanisms in the transition regions of interfaces [1] explains the intrinsic interdependence between mass and momentum transfer. Finally, a discussion of the peculiarities of resistances to mass transfer in boundary layers, based on the changes in molecular transport properties, is presented.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 161
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 200-208 
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: The catalytic properties of wide-pore zeolites, namely Ni- and Cu-doped faujastie H-Y and H-mordenite (H-M) are compared on the example of conversion of n-hexane. After thermal pretreatment of ion-exchanged zeolites, reduction with hydrogen (PH2 ≤ 40 bar) leads to a large number of metallic clusters and crystallites as well as ionic species in the zeolites. Notwithstanding this variety, the different types of catalysts can be divided into three classes: classical bifunctional catalysts (for example NiHM, NiHY) with ion exchange degrees 〉 30%, monofunctional catalysts, such as CuHM and CuHY with high copper contents (ion exchange degree 〉 40%) and metal-doped (Ni and Cu) zeolites which, depending on the conditions of pretreatment, act as bifunctional and/or monofunctional compounds and, therefore, show very unstable reaction behaviour. In addition to the extent of reduction, the cation distribution affects the activity and deactivation behaviour and, to a lesser extent, the product selectivity. The reaction mechanism of bifunctional catalysis is similar to that observed in platinum-doped catalysts, while the mechanism of monofunctional catalysis resembles the process on undoped zeolites.
    Zusätzliches Material: 11 Ill.
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  • 162
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 219-225 
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: This work investigates the thermodynamically based assumption that diffusion at binodal states of unstable fluid systems vanishes. It is shown experimentally that a scaling law, which describes the fall in diffusion near critical points, may also be applied in an extended form to its abatement at the limits of solubility. These results may profoundly affect the modelling of mass transfer between phases whose bulks exhibit states of saturation.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 163
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 240-247 
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: A systematic method of controller design is introduced to determine the overall charcteristic behaviour developed on process pole removal. The time delay compensation is automatically incorporated in the proposed control law. The implemented tuning parameters in the law are confined to the range between 0 and 1 to guarantee the stability of the overall control system. Subsequently, the fixed and adaptive control strategies are implemented to simulate a batch PVC reaction system. The adaptive control scheme provides good, roubust control of this simulated reactor notwithstanding the wide range of operating conditions and non-linear dynamics of the system. However, the fixed control scheme performs well only for a noise-free system. In addition, two limiting control laws, derived from the proposed method, are also used to simulate the reactor. The results indicate that these laws are not suitable for this non-linear reaction system.
    Zusätzliches Material: 13 Ill.
    Materialart: Digitale Medien
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  • 164
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: This article describes the effects which occur during three-component mass transfer in liquid-liquid extraction between saturated and undersaturated phases of the system glycerol-acetone-water. The description is based on experiments in a countercurrent spray column. The physical modelling starts with the balance equations of phase flows, taking into account the variation of concentrations and mass flow rates along the column axis as well as backmixing effects. In addition, recent findings on the mechanisms of mass transfer in saturated and undersaturated phasses, deduced from theoretical and experimental results, were used to formulate mass transfer coefficients. These are valid for the region near the interface of drops in a fluid and are inserted into the balance equations. A comparison between experiments and calculations of the observed phenomena is presented.
    Zusätzliches Material: 15 Ill.
    Materialart: Digitale Medien
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  • 165
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 275-287 
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Those chemical and photochemical characteristics of a photochromic system which are necessary for successful application to flow visualization studies in water are identified. The properties of a number of photochromic and photosensitive systems are discussed, and critically examined, with regard to these requirements.
    Materialart: Digitale Medien
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  • 166
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: This contribution demonstrates the possibility of using a thermodynamic description of electrolyte solutions directly for computer simulation of distillation columns. Coefficients are determined for a combination of a solvation model with a local composition equation for the activity coefficient. The use of one set of coefficients yields good results of calculation of vapour pressure, vapour phase composition and caloric data of hydrochloric acid. Solution of material and heat balance equations of distillation columns is achieved on an IBM PC with the above description. Two illustrative examples of an absorption and a rectification calculation are presented
    Zusätzliches Material: 12 Ill.
    Materialart: Digitale Medien
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  • 167
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: The knowledge of multicomponent adsorption equilibria is of great importance for the industrial design and application of adsorptive purification and separation processes. As the experimental determination of the required data is time-consuming and costly, theoretical help is desirable. This contribution presents and assesses the most common theoretical approaches to the calculation of multicomponent adsorption equilibria. The models are based on the assumption of an adsorbed solution, extension of the volume filling of micropores theory or statistical thermodynamics. These models are applied to different adsorptive/adsorbent systems with ideal and non-ideal equilibrium behaviour. It is established that, at low coverages of adsorbent surfaces, all theories provide good estimates of the adsorbed phase composition and total loading while, at high saturations, no model is completely satisfactory.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 168
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 347-352 
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: A simplified model has been developed to describe ammonia stripping process in spray towers. The effect of various operating parameters including air flow rate, contact time, droplet size, liquid to gas ratios and tower height on the performance of such systems has been studied in detail. The results obtained for ammonia stripping have been compared with the limited experimental data available in literature. The predicted results agree reasonably well with the reported experimental data.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 169
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 357-362 
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: The effects of particle size (layer thickness), BET surface area and pore size distribution on the reactivity of CaO derived from limestone were studied by using a pH-stat and the BET method. Visual analysis was obtained with SEM, and X-ray diffraction was used to determine the crystalline components present. It was found that the pore size distribution, including pore volume and pore surface distribution, affected the sulphatization behaviour. The larger pores (D 〉 50 Å) with their pore volume and pore surface were to some extent responsible for both initial reactivity and ultimate capacity of CaO.
    Zusätzliches Material: 19 Ill.
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  • 170
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 376-378 
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Activity coefficients of hydrocarbons and chloroparaffins at infinite dilution in methyl phenyl ether, butyl ether and methyl iso-butyl ketone at 293.15 K have been obtained by the retention-time method in a modified gas chromatograph. The experimental data are compared with predictions of the UNIFAC and MOSCED models. Selectivities for the 1,1,1-trichloroetane-1,2-dichloroetane separation process are reported.
    Zusätzliches Material: 1 Ill.
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  • 171
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: A semi-empirical gas-liquid equilibrium model for the absorption of CO2 in aqueous 3M AMP (2-amino-2-methyl-1-propanol) is presented. It applies to high CO2 loadings (y 〉 0.5) in the temperature range between 20 and 50 °C, and is based on experimental solubility and pH determinations. For a given amine concentration, it yields the equilibrium partial pressure of CO2 as a function of only two variables: the CO2 loading and temperature. The model correlates the expressions for the chemical equilibria involved as follows: pCO2 = m y × 10x, where pCO2 is the equilibrium partial pressure, x = logK - pH, m is the amine molarity, y the CO2 loading, and K is a parameter involving Henry's law constant, H, and the first dissociation constant, K1, of carbonic acid. pH is found to depend on both temperature and CO2 loading while logK depends only on the CO2 loadIng. Correlations for pH and logK are presented. The model fits own data for 3M AMP very well as well as the equilibrium data found in recent literature.
    Zusätzliches Material: 5 Ill.
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  • 172
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 63-71 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Many commercially important pigments such as titanium dioxide and carbonblack are produced as fumes from a combustion process. The fuming process generates open structured agglomerates conforming to a morphology predicated by physical considerations. For this reason widely different chemical pigments often manifest common physical structure. This structure can be characterized using the concepts of fractal geometry. In this communication the potential usefulness and physical significance of descriptive parameters of the agglomerate structure of fumed pigments based on the concepts of fractal geometry are explored. Similar structures present in high energy ceramic powders are discussed and the potential importance of fractal dimension parameters for the prediction of the physical behaviour of powders is outlined.
    Zusätzliches Material: 14 Ill.
    Materialart: Digitale Medien
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  • 173
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 86-89 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: A dispersed system is considered which will form its condensed phase at high temperatures and is characterized by a high density of very small supercritical nuclei. It is assumed that particle growth is determined by coagulation and (viscous flow) coalescence. The morphology of the final particles depends on the temperature history of the formation process. Compact spherical particles and agglomerates may be formed. Agglomerates result when the process temperature decreases to an extent that coalescence is quenched in the course of the growth process. The average size of the primary particles in the agglomerates is calculated by using the analysis and the approximations described in a previous paper. The growth kinetics of the primary particles are presented in a dimensionless form. The results show that the dimensionless size of the primary particles depends only on the ratio of two characteristic lengths of the system. For small values of this ratio, the size of the primary particles composing the agglomerates, although much greater than the initially formed nuclei, is independent of the volume fraction of the condensed aerosol. For large values of this parameter, the theory merges into the classical theory of perfectly coalescing spheres.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 174
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 100-100 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 175
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: A statistical analysis is made for the extinction of radiations in suspensions, whereby the whole range of possible particle concentrations is covered. The extinction signals are characterized by their average value and by a characteristic length of fluctuation. For simplicity, the considerations are restricted to geometric ray propagation in dispersions of perfectly absorbent, monosized spherical particles. An extinction equation is derived, which reduces to Lambert-Beer's law in the limit of low particle concentrations. For higher concentrations, significant deviations from Lamberg-Beer's law due to steric particle-particle interactions are predicted. The characteristic length of the fluctuations is a function of particle diameter and transmission and has a broad minimum with medium transmissions, allowing for maximum resolution with measurements in this range.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 176
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 105-109 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: The operational characteristics of cake-forming filter apparatus are strongly influenced by the structure of the dust cake formed. The quantitative evaluation of sectional images of loosely bound filter cake deposits is introduced. First the techniques with which the dust cake is prepared and with which scanning electron micrographs may be obtained are described, together with the subsequent digitization by video and computer equipment. This is followed by a comprehensive description of the evaluation of the digitized images, with special emphasis on the determination of the deposit's porosity and the computation of the particle and pore-size distributions at selected locations. Finally, results derived from a true filter cake are presented.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 177
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 101-104 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Some results are presented of investigations on the flow behaviour of very fine α-alumina powders having different particle size distributions. Shear tests were performed in a translation shear cell. The humidity was in the range 0.3 〈 pD/pSD 〈 0.6 in order to ensure the formation of adsorbed water layers only and to exclude capillary condensation. In the region of adsorbed layer bondings, the flow behaviour of very fine powders deteriorates in comparison with regions where no adsorption layers exist. An extrapolation of the unconfined yield strength for very low consolidation stresses results in an approximately constant value for different particle size distributions. In contrast, the slope of the linear function σc = f (σ1) increases with decreasing particle size up to a certain limit. For narrow particle size distributions, there is a pronounced decrease in the bulk density with decreasing particle size. Further, the bulk density is strongly influenced by the width of the distribution.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 178
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 142-150 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Test methodology has been developed to measure the particle removal efficiency of microporous membrane filtration media under conditions in which sieving is the dominant particle capture mechanism. The methodology was used to determine the particle capture efficiency of a 0.45 μm membrane filter for removal of submicrometer sized particles from DI water. Particle capture was found to be a strong function of particle diameter, filter media thickness, and filter loading. Particle removal efficiency increased with increasing particle diameter and media thickness. It decreased with increased filter loading when the filters were challenged with the smaller particles used in this study. Removal efficiency initially decreased then subsequently increased during loading with larger particles. Capture was independent of filtration velocity and particle concentration. A sieving model was developed to predict particle capture by the filter media as a function of particle diameter, filter thickness and filter loading. The model was found to accurately predict breakthrough of monodisperse particle suspensions through the media. Particle breakthrough occurred more slowly than predicted when the filters were challenged with a polydisperse particle suspension.
    Zusätzliches Material: 15 Ill.
    Materialart: Digitale Medien
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  • 179
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 173-173 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 180
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 170-172 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: British Standards committee GME/29/4 is concerned with “Particle sizing methods other than sieving”. Its work covers not only particle size distribution analysis but also methods of estimation of surface area and pore size distribution, as well as a glossary of terms relevant to those subjects. The current British Standards in the BS 3406 series (particle size analysis) and BS 4359 series (surface area) are reviewed, and a progress report is given on the status of several new and revised Standards which are in preparation.
    Materialart: Digitale Medien
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  • 181
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 164-169 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: An increased interest in the development of new techniques for fine grinding has resulted in a growing concern over the accuracy of size distributions for extremely fine particles. Since most particle size analyzers have lower detection limits, care must be taken when comparing size distributions which have not been properly mass balanced.An automated technique has been developed in which a completely mass balanced size distribution can be obtained using an Elzone 80XY particle size analyzer. A computer program is used to blend the data from successively smaller orifice tubes, and to determine the weight percent of material finer than the lower detection limit of the analyzer. This result is then used to correct the distribution for the missing fine material. Experimental results indicate that size distributions obtained using this procedure are reproducible and compare favorably with those obtained using other size analysis techniques.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 182
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 173-174 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 183
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 200-208 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: An automatic measuring system was developed to perform simultaneous measurements of particle size and charge distributions in a clean room and other aerosol sources. The system consists of an electrostatic condenser (EC) and an optical particle counter (OPC), which are controlled by a personal computer (PC). The PC automatically varies the voltage on the EC and converts the corresponding OPC counts to charge distributions. The reliabilities of the data inversion method and the automatic measuring system were confirmed by theoretical and experimental examinations, respectively. In the theoretical examination, inverted charge distributions were tested and compared with various assumed input distributions. In the experiment where monodisperse aerosols neutralized by a 85Kr neutralizer were used, the measurement results agreed well with the theoretical Boltzmann charge distribution. The application of this technique is demonstrated by the measurement of charge and size distributions of aerosols in a clean room.
    Zusätzliches Material: 14 Ill.
    Materialart: Digitale Medien
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  • 184
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 274-281 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Quasi-elastic light scattering, elastic light scattering and Fraunhofer diffraction can be used for optical particle sizing. Simulated data were used to compare the different scattering techniques in terms of resolution and range of applicability. Elastic scattering techniques have a ten times higher resolution but cover a smaller size range than quasi-elastic light scattering. The most important inversion techniques for data evaluation for such experiments were also compared. Regularization techniques with positivity constraints and interpolating cubic B-splines proved to be superior to truncated singular value decomposition and maximum entropy methods.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 185
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 259-266 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: The measurement of polydisperse populations of colloidal particles with quasielastic light scattering (QLS) is a common and dangerous practice. Here intensity autocorrelation functions with different linewidth distributions are simulated. The simulated data are treated with the histogram and exponential sampling methods and the results are contrasted with the results of the Laplace inversion routine of Provencher. All methods work well in calculating the size distribution from noise-free correlation functions. In analyzing noisy data the methods may produce results that bear no relation to the true size distribution. The histogram method fails to determine size distributions from noisy simulated and real correlation functions. The exponential sampling method gives a qualitative measure of the size distribution when the required resolution does not exceed the limitations set by noise theory. Provencher's routine extracts smooth unimodal distributions very accurately even from noisy correlation functions, but determination of bimodal distributions may be unreliable. The importance of taking data at many scattering angles is emphasized and experimentally determined size distributions of samples of polystyrene latex spheres measured at multiple scattering angles are presented.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 186
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 287-293 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: The range of the parameters of the Nukiyama-Tanasawa distribution function was analysed, leading to the identification of the physically relevant parameter space. The analysis was also applied to the Rosin-Rammler distribution function.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 187
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 282-286 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Dynamic light scattering is a technique used for the optical determination of a colloidal particle size distribution. A simple procedure, based on a trapezoidal model for the linewidth distribution function, is given for obtaining a constrained regularized inversions of correlation data obtained in dynamic light scattering experiments, and estimating the accuracy of such inversions. Based on the eigenfunction decomposition of the Laplace integral equation, error bars, which are directly related to the accuracy of the correlation data, may be placed on both analytical and discrete inversions. By using a regularization procedure, and a nonnegativity constraint, problems with statistical noise in data may be handled effectively.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 188
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 294-296 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: The calibration of electrical sensing zone instruments is normally achieved by using spherical particles with a certified size. An alternative and more fundamental procedure, known as mass or self-calibration, is to use particles of the material under test.This work concerns the mass calibration technique, in particular the equations used to calculate the mass calibration constant. It is demonstrated that some of the published expressions are inconsistent. An expression particularly suitable for the Coulter Counter Model ZM has been derived and validated. Some experiments were also performed using irregular particles, in order to compare both calibration methods.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 189
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 297-300 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: A miniaturized droplet generator with some new features, working on the principle of laminar liquid jet instability and break-up was designed. The instrument has been used to study the dispersion of monosized droplets in a turbulent swirling flow, exhibiting the main features of combustion chamber flows of modern gas turbines.The operating range of the generator was evaluated by phase-Dopper anemometry (PDA). It was demonstrated that the device also works in some metastable operating modes, producing coherent droplet streams with very small standard deviations for drop size and drop velocity. Special attention was directed to the reliability of the device and to the control of drop size. The PDA measurements showed that, in contrast to the evaluated optimum excitation frequency, the drop size cannot be determined from the orifice diameter.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 190
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 301-307 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: For many years efforts have been made to describe the complex process of particle separation in cyclones, and a multitude of separation models have been set up. A comparison of such separation models fails because insufficient usable test results are available and systematic and precise investigations are missing.It is important for the design of cyclones to rate their separation properties by means of the fractional collection efficiency. On account of the known measuring problems, the data supply of reliable fractional efficiency curves of cyclones is still too small. Fractional efficiency as a function of the entrance velocity was measured with a high-speed optical measuring technique. Measurements of low dust concentrations are presented. Geometrically similar cyclones of four different sizes were investigated. The fractional efficiency curves are plotted versus dimensionless parameters and the validity of the design criteria gained in this way is shown. The influence of particle shape on the fractional efficiency curves is discussed.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
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  • 191
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 323-323 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 192
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 8 (1991), S. 308-314 
    ISSN: 0934-0866
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Maschinenbau , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: An experimental study of the filtration performance of several commercially available, NIOSH-approved, disposable respirators was conducted using monodisperse DOP and NaCl particles with diameters in the 0.035 to 4 μm range.The aerosol penetration through the respirators were measured at flow rates of 16, 28 and 48 L/m using a condensation nucleus counter, an aerodynamic particle sizer, and a laser optical particle counter for purposes of comparison. The results obtained by these instruments were found to be in good agreement with each other in the overlapping region of particle size of the instruments.The peak penetration through the respirator filters was found to range from approximately 1.2% to 30% at 16 L/m, 3.5% to 37% at 28 L/m, and 6% to 45% at 48 L/m. The most penetrating particle size was found to lie in the 0.1 to 0.4 μm diameter range. Further, no significant difference in penetration for NaCl and DOP particles was found, suggesting that the particlebounce effect was not important in the present study.
    Zusätzliches Material: 15 Ill.
    Materialart: Digitale Medien
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  • 193
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 11-19 
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Inclined plates are often installed as mechanical separation aids in gravity settlers for the separation of liquid-liquid systems. The authors investigated the process of coalescence of single drops on trickling films flowing off inclined plates. The method of investigation was developed by Blass and Rautenberg. It ensures that, under certain conditions, only hydrodynamic parameters influence the coalescence process to any significant extent. The coalescence time of the drops characterizes the process of coalescence. Short time between 1 and 3 seconds provide favourable conditions for coalescence whereas long times, often ten times as long or even longer are unfavourable. This contribution introduces a criterion for clear demarcation between these two ranges and also a determination of separation parameters for favourable conditions for coalescence. Furthermore, the function of the plates is described, which is determined by hydrodynamic and wetting processes. The characteristic operating regions of a plate are shown in a working diagram.
    Zusätzliches Material: 13 Ill.
    Materialart: Digitale Medien
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  • 194
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: When declaring and using process engineering data such as, for exmple, mixing times or kLa values, it is assumed that these apply to the entire reactor contents. The condition of uniform mixing, necessary for this, is generally met in the regime of turbulent flow. When highly viscous and, above all, strongly non-Newtonian liquids are stirred in small reactors, there are frequently also regions of laminar flow and completely stagnant zones, which are only partially mixed or not at all. The present paper pursues the question to what extent is the gas-liquid mass transfer in stirred, highly non-Newtonian liquids influenced by the mixing behaviour of the reactor. The results show that, below certain Reynolds numbers, three relatively distinct regions exist, with different mixing intensities. Between an almost ideally mixed region in the vicinity of the stirrer and a completely stagnant and dead one, there is a zone of very slight motion. This finding demonstrates that the usual determination of integral or volume-based data in the literature is neither logical nor adequate for the case under consideration. Thus, the gas-liquid mass transfer takes place mainly in the relatively well mixed region. Therefore, use of a kLa value also requires the volume of this region to be declared. Only the knowledge of this volume enables us to correlate the kLa values in such a way that the sorption characteristics thus obtained appear suitable for scale-up. This procedure, which is illustrated by numerous examples of measured results for different stirrers, is important whenever design data for highly viscous liquids are to be worked out on the basis of laboratory measurements. Only when larger equipment is used, in which turbulent flow can be achieved, this problem does not arise because of the relatively uniform mixing of reactor contents.
    Zusätzliches Material: 20 Ill.
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  • 195
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 89-95 
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: The correct choice of packing is of decisive importance for optimum process efficiency in the operation of two-phase countercurrent columns. An important criterion for this choice is the pressure drop in the gas flow. Theoretical relationships are derived for calculating the pressure drop in beds with dry and trickle packings. It has been demonstrated by comprehensive experiments that these relationships allow the pressure drop to be determined more accurately than by previous methods. The experiments were performed at the Department of Thermal Separation Processes of Bochum University on 54 different packed beds, using 24 different systems.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 196
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: A multipurpose apparatus was designed, built and operated with the aim of a simultaneous determination of enthalpy of mixing, heat capacity, kinematic viscosity and density of liquid mixtures at 240 〈 T 〈 370 K and 1 〈 p 〈 25 bar. Its operation was monitored by a PC. Details of design and the first experimental results are presented.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 197
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: The application of dynamic programming using an interative procedure, which employs domain contraction and accessible grid points for the state vector, is investigated for solving optimal control problems where the system is described by a set of difference equations. A model of a gas absorber with six state variables and two control variables is used to examine the feasibility of the proposed algorithm and to analyze the effects of the grid size and of the domain contraction factor. This algorithm yields rapid convergence to the optimum even when a relatively coarse grid with as few as 11 grid points is used.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 198
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991) 
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
    BibTip Andere fanden auch interessant ...
  • 199
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: The number fraction of drops of a given size which break up at rotor level in a rotating disc contactor has been observed during mass transfer in either direction to or from solvent or aqueous drops. Critical rotor speeds for a given drop size undergoing mass transfer can be used to find an effective interfacial tension. Using this interfacial tension value, the break-up fractions are correlated within experimental uncertainties in the same manner as for no mass transfer. Drop break-up fractions depend on column size and relevant empirical correlations of the data are presented. The results may be used to estimate the effect of mass transfer on drop size distributions in an RDC.
    Zusätzliches Material: 17 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 200
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 14 (1991), S. 209-212 
    ISSN: 0930-7516
    Schlagwort(e): Chemistry ; Industrial Chemistry and Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: The non-steady-state behaviour of a fixed bed reactor controlled by periodical direction reversal of reactant feed, applied in catalytic oxidation of industrial waste gases, containing organic compounds and carbon monoxide, has been investigated. The effects of the type of oxidized compound, its initial feed concentration, linear gas velocity, inerts-to-catalyst ratio and inerts thermophysical characteristics on the formation of reactor concentration and temperature fields were elucidated. It was shown that autothermal reactor behaviour is guaranteed by concentrations of the oxidized component which ensure an adiabatic temperature increase in excess of 20 °C. Deviations of either flow rate or initial concentration of the oxidized compound do not disturb the operational stability.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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