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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 19-29 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A procedure for identifying redundancy in the Cartesian force constant matrix is described, and a prescription is given for generating the entire matrix of second derivatives from the minimal set of information. A proof is supplied which demonstrates that the number of nonredundant rows corresponding to a symmetry unique atom is necessarily less than three if the atom is invariant with respect to a symmetry operation of the point group other than the identity or inversion. Furthermore, only one row is required if the atom lies on a threefold or higher-order rotation axis. An application of the procedure to the evaluation of harmonic force constants by numerical differentiation of gradient vectors is briefly described.
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  • 2
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    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 31-45 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An intermediate neglect of differential overlap (INDO) model for elements of the second transition series is described. Values of exponents for the radial portion of the Slater basis atomic orbitals, the orbital ionization energies, and the beta (or bonding) parameters for these elements are reported. Use of the model to investigate equilibrium geometries, relative energy ordering of geometric isomers, spectroscopic transition energies, energy ordering of state wave functions of different symmetry, trends in dipole moments, and equilibrium stretching frequencies is reported. The results indicate that the INDO method is capable of yielding quality results for species containing atoms of the second transition series.
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  • 3
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    International Journal of Quantum Chemistry 39 (1991), S. 625-645 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The numerical properties of a two-dimensional integral representation [J. Grotendorst and E.O. Steinborn, Phys. Rev. A 38, 3857 (1988)] of the three-center nuclear attraction integral with a special class of exponential-type orbitals (ETO'S), the B functions [E. Filter and E.O. Steinborn, Phys. Rev. A 18, 1 (1978)] are examined. B functions span the space of ETO'S. The commonly occurring ETO'S can be expressed in terms of simple finite sums of B functions. Hence, molecular integrals for other ETO'S, like the more common Slater-type orbitals, may be found as finite linear combinations of integrals with B functions. The main advantage of B functions is the simplicity of their Fourier transform that makes the derivation of relatively simple general formulas for molecular integrals with the Fourier transform method possible. The integrand of the integral representation mentioned above shows sharp peaks causing, in the case of highly asymmetric charge distributions, slow convergence of the quadrature method used by Grotendorst and Steinborn. New quadrature schemes are presented that use quadrature rules based on Möbius transformations. These rules are well suited for the numerical quadrature of functions that possess a sharp peak at or near a single boundary of integration [H.H.H. Homeier and E.O. Steinborn, J. Comput. Phys., 87, 61 (1990)]. Numerical results are presented that illustrate the fact that convergence of the new quadrature schemes is about a factor two faster in case of highly asymmetric charge distributions.
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  • 4
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    International Journal of Quantum Chemistry 39 (1991), S. 681-688 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An orbital transformation that minimizes the sum of the squares of the off-diagonal Hamiltonian elements between the singly excited configurations is described. The resulting single-excitations-adapted molecular orbitals (SEAMOS) are found to be very suitable for the description of electronic excited states. The test calculations on the singlet and triplet excited states of the N2, CO, and H2CO molecules are presented.
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  • 5
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    International Journal of Quantum Chemistry 39 (1991), S. 709-727 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A theoretical model based on physical, chemical, and biochemical mechanisms has been presented to evaluate the yields of DNA strand breaks (single and double) as a function of linear energy transfer (LET) or -dE/dx. Energetic heavy charged particles are considered explicitly to provide a general theory for low- as well as for high-LET radiation. There are three main features of the calculation: (a) track structure considerations for the energy deposition pattern, (b) three-dimensional structure of DNA molecules to provide information on the exact location of damage, and (c) a Monte-Carlo scheme to simulate the diffusion processes of water radicals. To avoid the complexities of a cellular medium, an aqueous solution of DNA is considered in the calculation. When the results of the calculations are compared with experimental measurements of the yields of strand breaks in mammalian DNA (exposed in a cellular complex), reasonable agreement is obtained. However, only those experimental data have been compared where there were no enzyme repair processes. The method of calculation has also been extended to study breaks in higher-order structures of DNA molecules such as chromatin. Specific limitations of the present model have been pointed out for making further improvements.
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  • 6
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    International Journal of Quantum Chemistry 39 (1991), S. 767-786 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electronic aspects of the catalytic mechanism of liver alcohol dehydrogenase (LADH) are studied with the help of ab initio analytical gradient SCF MO methods. Three points are considered: (i) role of the catalytic zinc; (ii) geometry and electronic structure of the transition state for the hydride transfer reactions; and (iii) factors affecting the energy gap for the hydride transfer step, namely, substrate binding to zinc, reaction field, and serine 48 effects on the potential energy profile. The coordination sphere of the catalytic zinc has been modeled with an ammonia molecule and two SH- groups; complexes with CH3O-, CH3OH, and CH2O have been studied; a (6, 2, 2, 2, 1/6, 2, 1/3, 2) basis set has been used for Zn++; a (5, 2, 1, 1/3, 2) was used for oxygen, carbon, and sulfur; and a (3, 1) was used for hydrogen atoms. The hydride step was studied with two model systems: pyridinium cation/1,4-dihydropyridine coupled to the CH3O-/CH2O reaction, and cyclopropenyl cation/cyclopropene coupled to the CH3O-/CH2O system. For the latter, the role of Ser48 has been studied at the supermolecule level. The calculation on the hydride transfer step has been done at a 4-31G basis set level. The results obtained shed new light on the sources of catalytic activity of liver alcohol dehydrogenases.
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  • 7
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    International Journal of Quantum Chemistry 39 (1991), S. 839-849 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present a treatment of chemisorption that uses the Green matrix of the surface and the admolecule, as well as a cluster calculation of a small surface cluster. Since full HF-SCF-band structures with nonlocal exchange are available now for larger systems for a couple of years, it is possible to treat the substrate surface and the admolecule on equal footing. This offers a natural way to solve the embedding problem. We have applied the formalism to the adsorption of H2 on beryllium and show that in contrast to cluster calculations there appears a binding, which is experimentally verified.
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  • 8
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    International Journal of Quantum Chemistry 39 (1991), S. 211-226 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electronic absorption spectra of 2-, 3-, and 4-vinylpyridines and 1,2-(2,3-dipyridyl), 1,2-(2,4-dipyridyl), 1,2-(3,4-dipyridyl), and 1,2-(4,4-dipyridyl) ethylenes have been investigated in polar and nonpolar solvents. A correlation has been made between the geometry of the molecule and the observed spectrum. Molecular orbital calculations have been carried out using the INDO/S—CI procedure and a limited geometry optimization. The solvent effect at the MO level has been calculated. MO calculations predicted the existence of nπ* transitions that were not observed experimentally. The wave functions of the different CI states were calculated. The experimental transition energy as well as oscillator strength corresponded satisfactorily with the calculated ones. The observed transitions were assigned according to the results of MO calculations.
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  • 9
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    International Journal of Quantum Chemistry 39 (1991) 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 10
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    International Journal of Quantum Chemistry 39 (1991), S. 251-267 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: From the speculations of G. N. Lewis in 1916, [J. Am. Chem. Soc. 38, 762 (1916)], the spectral predictions of R.S. Mulliken [Nature 122, 505 (1928)], and the quantum mechanical treatment by E. Hückel [Z. Phys. 60, 423 (1930)], the three lowest states of molecular oxygen (3Σg-, 1Δg, and 1Σg+) remained spectroscopic elusives until Gerhard and Lisa Herzberg [G. Herzberg, Nature 133, 759 (1934); L. Herzberg and G. Herzberg, Astrophys. J. 105, 353 (1947); G. Herzberg and L. Herzberg, Astrophys. J. 108, 167 (1948)], precisely defined them by observed infared transitions. The excited singlets remained of interest mainly to atmospheric spectroscopists and astrophysicists, and research on these species was scarce. The discovery in 1963 by A.U. Khan and M. Kasha [J. Chem. Phys. 39, 2105 (1963)] of the simple chemical production of singlet molecular oxygens by the aqueous reaction of hydrogen peroxide and hypochlorite released an explosion of research on the neglected species. Fifteen research symposia and research treatises confirm the broad range of chemical activities of singlet oxygen. The extension to biological systems is now proceeding, with surprising evidence of involvement of natural processes, including the action of singlet oxygen in white blood cell phagocytosis.
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  • 11
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    International Journal of Quantum Chemistry 39 (1991), S. 371-386 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We propose 10 desirable features or criteria for general purpose methods to be applied to the calculation of a range of spectroscopic properties. We discuss the second-order polarization propagator approximation (SOPPA) in light of these criteria by giving the actual computational expression used as well as a few numerical examples taken from the theory of NMR spectra (magnetic shieldings and spin-spin coupling constants). We demonstrate that SOPPA comes close to fulfilling these criteria.
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  • 12
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    International Journal of Quantum Chemistry 39 (1991), S. 423-436 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method for analyzing asymmetric top rovibrational bands displaying both blended and resolved features is described. The two-phase computational procedure uses a modified version of the asymmetric rotor-band contour program FASTPLOT to generate a preliminary set of upperstate spectroscopic constants. The parameters are subsequently refined by employing the assigned line-fitting formalism of the ASYROT program using both resolved and blended features. The technique is detailed in a comprehensive analysis of the ν17 band of pyridine. Inclusion of quartic centrifugal distortion constants was found to satisfactorily model a high-resolution (0.004 cm-1) spectrum of this band, yielding a standard deviation of 0.00137 cm-1. The variation in the rotational parameters with vibrational quantum number is examined in terms of possible weak rovibrational perturbations to the ν17 state. An ab initio calculation of the ν17/ν27 Coriolis coupling constant indicates the observed results are consistent with the interaction of these two vibrational states.
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  • 13
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    International Journal of Quantum Chemistry 39 (1991), S. 521-521 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 14
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    International Journal of Quantum Chemistry 39 (1991), S. 173-181 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An original procedure has been developed to determine the eigenvalues and the eigenfunctions of quantum-mechanical many-body systems with a harmonic oscillator interaction. Exact solutions in the explicit form have been obtained for the case of systems containing three groups of identical particles. For the system containing two groups of identical particles, a solution in the adiabatic approximation has been obtained and compared with the exact one.
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  • 15
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    International Journal of Quantum Chemistry 39 (1991), S. 229-229 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 16
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    International Journal of Quantum Chemistry 39 (1991), S. 233-233 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 17
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    International Journal of Quantum Chemistry 39 (1991), S. 331-344 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 18
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    International Journal of Quantum Chemistry 39 (1991), S. 1-2 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 19
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    International Journal of Quantum Chemistry 39 (1991), S. 93-113 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The excitation and ionization spectra of RuO4 and OsO4 are studied theoretically by the symmetry-adapted cluster (SAC) and SAC-CI theories. This is the attempt to assign whole of the spectra by ab initio calculations including electron correlations. In the ground state, electron correlations work to reduce the polarity of the M-O bond overestimated in the Hartree-Fock calculation. The Os-O bond is stronger than is the Ru-O bond, which is reflected in the differences of the excitation and ionization spectra of RuO4 and OsO4. The excitation energies of the experimental spectra are well reproduced by the SAC-CI theory, though the calculated intensities of some peaks are very small in comparison with the experiments. The outer-valence ionization spectra calculated by the SAC-CI theory agree well with the experimental photoelectron spectra. Some shake-up peaks that are accompanied with an electron-transfers from oxygen to metal are also calculated.
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  • 20
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    International Journal of Quantum Chemistry 39 (1991), S. 159-162 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dependence of the rainbow angle on the depth of the potential well, the equilibrium distance, andthe force constant of the potential are discussed for several potential functions.
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  • 21
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    International Journal of Quantum Chemistry 39 (1991), S. 183-196 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An exact, within the Born-Oppenheimer approximation, body-fixed Hamiltonian for the nuclear motions of a triatomic system is presented. This Hamiltonian is expressed in terms of two arbitrarily defined internal distances and the angle between them. The body-fixed axis system is related to these coordinates in a general fashion. Problems with singularities and the domain of the Hamiltonian are discussed using specific examples of axis embedding. A number of commonly used coordinate systems including Jacobi, bond-length-bond-angle, and Radau coordinates are special cases of this Hamiltonian. Sample calculations on the H2S molecule are presented using all these and other coordinate systems. The possibility of using this Hamiltonian for reactive scattering calculations is also discussed.
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  • 22
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    International Journal of Quantum Chemistry 40 (1991), S. 1-2 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 23
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    International Journal of Quantum Chemistry 40 (1991), S. 33-53 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A behavior of a quantum rigid and pointlike dipole in a permanent electric field is under study. A dependence of a number of librational energy levels on the strength of the electric field is investigated on the basis of some rigorous results for the appropriate normal Jacobian matrices.
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  • 24
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    International Journal of Quantum Chemistry 40 (1991), S. 139-148 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A very simple modification of the usual (∼N4) SCF procedure is proposed, permitting the exclusion of basis set superposition errors (BSSE) in problems of intermolecular interactions. No a posteriori corrections are required. The results of this “CHA/F method” are numerically close to those of the Boys-Bernardi correction scheme but are free from the “overcompensation” characteristic of the latter at smaller distances.
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  • 25
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    International Journal of Quantum Chemistry 40 (1991), S. 243-264 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The singly excited functions satisfying Brillouin theorem are expressed as linear combinations of configuration-state functions for any spin and spatial symmetries (atomic or molecular) and for any reference wave function. The generality of the formulation is ensured by the use of the irreducible tensor method that can be adapted to any symmetry point group of interest. The expansion coefficients are simply written as products of fractional parentage coefficients, spin- and orbit-recoupling coefficients, and phase factors. The formalism is illustrated for some atomic (Kh) and molecular (C∞v, C3v, and Td) configurations. Group theoretical techniques are also used to correlate the Brillouin conditions within a chain of groups.
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  • 26
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    International Journal of Quantum Chemistry 40 (1991), S. 299-304 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A model for catecholamine storage in vesicles is analyzed within the SCRF-CNDO/2 approach including continuum solvent effects. The model considers the approach of cationic norepinephrine (NE) to a positively charged guanidinium moiety. Ion-pair formation is found for the whole range of dielectric constants. Even though stable states of H-bonded partners are found for large dielectric constants, this process is ruled out to occur because it involves too high energies. It appears that the medium's polarity is determinant in lowering the energy barrier between the ion-pair complex and the separated partners. Thus, as the medium dielectric constant increases, the equilibrium between the two states is enhanced.
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  • 27
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    International Journal of Quantum Chemistry 39 (1991), S. 519-519 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
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  • 28
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    International Journal of Quantum Chemistry 39 (1991), S. 487-517 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present a general method of implementing the kinetic balance condition within the Dirac-Fock (DF) self-consistent field (SCF) formalism for closed-shell molecular structure. We review the steps leading to the derivation of DF SCF equations for closed-shell molecules, particularly as formulated by Matsuoka et al. In the present approach, the large component of the molecular spinors are expanded in terms of atomic basis spinors of spherical-type Gaussian functions, with the small component related to the large component by the kinetic balance condition. It is shown that imposing the kinetic balance condition on geometric Gaussian-type basis functions allows us to obtain the Fock matrix elements, involving both the large and the small components, form the standard nonrelativistic Cartesian-type matrix elements. By using properties of orthogonal polynomials, the solid spherical harmonics are expressed in Cartesian form, thus providing a general basis for transformation of one- and two-electron-matrix elements, obtained from a Cartesian Gaussian-type basis, to a spherical Gaussian-type basis. The advantages of using kinetically balanced geometric Gaussian-type basis functions in molecular DF calculations including finite-size nucleus effects are emphasized. For the sake of completeness, we have added in an appendix corrections to the nuclear attraction matrix elements for the finite-size nucleus already derived by Matsuoka.
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  • 29
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Recently we extended our strategy for MRD-CI (multireference double excitation-configuration interaction) calculations, based on localized/local orbitals and an “effective” CI Hamiltonian, for molecular decompositions of large molecules to breaking a chemical bond in a molecule in a crystalline or other solid environment.Our technique begins with an explicit quantum chemical SCF calculation for a reference molecule surrounded by a number of other molecules in the multipole environment of more distant neighbors. The resulting canonical molecular orbitals are then localized, and the localized occupied and virtual orbitals in the region of interest are included explicitly in the MRD-CI with the remainder of the occupied localized orbitals being folded into an “effective” CI Hamiltonian. The MRD-CI calculations are then carried out for breaking a bond in the reference molecule. This method is completely general in that the space treated explicitly, as well as the surrounding space, may contain voids, defects, deformations, dislocations, impurities, dopants, edges and surfaces, boundaries, etc.Dimethylnitramine is the smallest prototype of the energetic R2N - NO2 nitramines, such as the 6-member ring RDX or the 8-member ring HMX. Decomposition of energetic compounds is initiated in the solid by a breaking of the target bond. Thus, it is crucial to know the difference in energy between breaking a bond in an isolated energetic molecule versus in the molecule in a solid. In the present study, we have carried out MRD-CI calculations for the Me2N - NO2 dissociation of dimethylnitramine in a dimethylnitramine crystal. The cases we investigated were one dimethylnitramine molecule (surrounded by 53 and 685 neighboring dimethylnitramine molecules represented by multipoles), three dimethylnitramine molecules, and three dimethylnitramine molecules (surrounded by 683 neighbors). All multipoles were cumulative atomic multipoles up through quadrupoles. The MRD-CI calculations on dimethylnitramine required large numbers of reference configurations from which were allowed all single and double excitations.
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    International Journal of Quantum Chemistry 39 (1991), S. 667-679 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The frequency-dependent dipole polarizability, α(E), is calculated using the second-order polarization propagator approximation (SOPPA). We have shown how to express α(E) as a function of E2 and thus obtained a form of α(E) that can be used to compute C6-coefficients without invoking complex arithmetic. For He we find that SOPPA recovers a large fraction of the correlation contribution for all frequencies, whereas for H2 where the correlation contributions are much smaller and also basis set-dependent, we find a less definite trend of SOPPA relative to RPA.
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    International Journal of Quantum Chemistry 39 (1991), S. 71-91 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The usefulness of the MS-Xα method for calculating molecular transition properties is investigated in a study of NO2. Two-dimensional potential surfaces are obtained in C2v symmetry for the X̃2A1/Ã2B2 system. Potential curves that approximately follow the asymmetric stretch coordinate are also presented: On investigation, no symmetry-broken solutions were found. At all nuclear geometries investigated, the muffin-tin sphere radii were chosen by an energy-minimization technique. The inclusion of corrections to the muffin-tin form of the Xα total energy is shown to be essential, if the computed surfaces are to be qualitatively correct. The transition dipole moment connecting the two states is evaluated as a function of nuclear coordinates, using the transition-state approximation. Finally, the radiative decay of a single vibronic level in NO2 is modeled and the relevance to experiment is discussed.
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    International Journal of Quantum Chemistry 39 (1991), S. 131-147 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nonempirical quantum chemical method Hartree-Fock-Roothan LCAO SCF MO in a two-exponent Dunning basis with the use of an extended set of Gaussian functions by Huzinaga-Dunning with consideration of electron correlation according to the Meller-Plesset theory of excitations of the second order was used to study monohydrates of Li+, Na+, K+, and HCOO- ions. The indicated basis was supplemented with polarization functions of d-type on the O atom and of p-type on the hydrogen atom as well as with diffusion functions of p-type on the oxygen atom. It has been found that binding energies of the water molecule with Li+, Na+ appeared to be higher and with K+ lower than with HCOO- · H2O. Potential curve shapes of K+ + H2O and HCOO- + H2O reactions are shown to be similar. The molecular mechanism of K+ channel selectivity of an excitable membrane is explained on the basis of the obtained calculations.
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    International Journal of Quantum Chemistry 39 (1991), S. 287-298 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In flow tube studies of the quenching of O2(b1Σg+), broad band emission of O2(b):M collision complexes was found to appear under the discrete rotational lines of the 0-0 band of the b1Σg+ → a1Δg electric quadrupole transition at higher oxygen pressures and on addition of foreign gases. Bimolecular rate constants for the collision-induced emission processes have been derived from the ratio of the intensities of the discrete lines and the continuum as well as from low-resolution measurements of the relative intensities of the b → a and b → X bands as a function of O2 and added gas pressure. They range from ≈10-21 cm3 s-1 for He to ≈4 × 10-19 cm3 s-1 for PCl3 vapor.
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    International Journal of Quantum Chemistry 39 (1991), S. 523-539 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present a model system for the study of curve-crossing situations in diatomic molecules. All model parameters are determined by the potential energy topology. No coupling functions are fitted. The standard approximation schemes (Born-Oppenheimer approximation, adiabatic approximation, and the generator coordinate approximation) are then applied. The result of these numerical experiments suggest that the generator coordinate approximation is able to remove 80%-90% of the nonadiabatic effect on all levels throughout the crossing region.
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    International Journal of Quantum Chemistry 39 (1991), S. 593-604 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An expression for the product of a single-cycle class [(1)N - P(p)]N and an arbitrary class [(1)l1(2)l … (N)lN]N of the symmetric group has recently been conjectured. This expression involves a sum over a relatively small number of reduced class sums, depending on p indices. A further conjecture is formulated and demonstrated, according to which reduced class coefficients (RCCS) involving cycles whose length is expressed by means of a single index can be related to corresponding coefficients in the product of [(1)N - P+1(p - 1)]N with an arbitrary class sum. Consequently, the problem of evaluating the general class sum product reduces to that of obtaining a relatively small set of fundamental RCCS containing no single-index cycles. The conjectures mentioned can be used to evaluate the product [(1)N - p(p)]N · [(1)N - q(q)]N in terms of fundamental RCCS that can all be obtained from the product [(r)]r · [(r)]r, where r = min(p, q). For the latter product, we use a result due to Boccara.
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    International Journal of Quantum Chemistry 39 (1991) 
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    International Journal of Quantum Chemistry 39 (1991), S. 647-647 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    International Journal of Quantum Chemistry 39 (1991), S. 345-352 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The near-ultraviolet spectrum of a dinaphthonorbornadiene is reported and is interpreted using simple exciton theory that treats this molecule as a dimer of naphthalene. It shows examples of weak, intermediate, and strong coupling for the interaction of the three observed bands of naphthalene.
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    International Journal of Quantum Chemistry 39 (1991), S. 387-397 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Coherent dynamics of multilevel systems is of interest for the elucidation of energy disposal and multiphoton chemistry of polyatomic molecules. We compare the analytical solutions for coherent multiphoton excitation of two sparse multilevel model systems: (1) The spin-J system consisting of N = (2J + 1) equally spaced levels with the radiative coupling being determined by the xth component of the angular momentum. (2) The equally coupled N level system. The transition amplitudes for system (1) are always periodic, which is in contrast to the nonperiodic behavior exhibited by system (2) for N 〉 3.
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    International Journal of Quantum Chemistry 39 (1991), S. 437-447 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A formulation is presented of the effects of van der Waals interaction on infrared intensities. The theory takes account of induction and dispersion interactions (including charge interpenetration) and is applicable to fluids of arbitrary density. The transition moments are developed from generalized van der Waals-induced moments, and expressions are obtained for the adsorption coefficient in terms of generalized charge densities and charge-density (hyper)susceptibilities. Explicit expressions are given also of the integrated absorption coefficient in terms of multipoles, and (hyper)polarizabilities and their derivates, and the usefulness of this formulationin interpreting experimental data is illustrated by several examples. The relevance of the induction and dispersion interactions to allowed and to forbidden transitions made allowed is discussed.
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    International Journal of Quantum Chemistry 39 (1991), S. 455-486 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: The interaction between theory and experiment in the field of molecular core electron spectroscopies is reviewed. Those aspects that distinguish the theoretical descriptions of core and valence electron spectra are analyzed in particular. Differences in the theoretical approaches to atomic and molecular spectra in terms of scattering and many-body theories are commented on. The molecular core electron spectroscopies are analyzed from a common point of view with respect to molecular orbital theory, many-body theory, and the role of localization and local selection rules. A brief analysis is presented for the particularities that enter the calculations of core hole spectra. Solutions are described to computational problems posed by the quasi-bound, highly excited nature of core hole states and by the large electronic relaxation following their creation. Two areas where the interaction between theory and experiment is particularly fruitful are briefly reviewed, namely, the theory of vibronic excitations in core electron spectra and the theory of the core photoelectron chemical shift.
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    International Journal of Quantum Chemistry 39 (1991), S. 585-592 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: A non-local generalization K(r, r') of the kinetic energy t(r) such that t(r) = ∫K(r, r') dr' is defined using the idempotency property of the Hartree-Fock first-order density matrix. This is, in turn, related by means of an explicit differential equation to the non-local exchange energy density X(r, r'). The relationship is illustrated for a couple of examples: with the Fermi-hole in a uniform electron gas, of importance in the local density version of density functional theory, and with inhomogeneous electron systems.
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    International Journal of Quantum Chemistry 39 (1991), S. 605-613 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: The total energies, in the Hückel theory, of a large number of polyhex molecules and some containing a four-membered ring have been calculated and analyzed. The results confirm that within a set of isomers the number of Kekulé structures is the dominant variable. It is proposed that this term should be recognized as the aromatic term. The remaining contributions to the energy can be attributed to local features of the molecule. Comparison with the Hess-Schaad analysis of the same energies indicates that this treatment is simpler, more complete, and closer to the original concept of aromaticity.
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    International Journal of Quantum Chemistry 39 (1991) 
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    International Journal of Quantum Chemistry 39 (1991), S. 11-17 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: The common quantum mechanical problem for the total class of saturated hydrocarbons has been stated and solved within the framework of the effective Hamiltonian method. A quantum mechanical substantiation of the transferability of the electronic structure characteristics (bond dipole moments, bond energies, and bond force constants) as well as the investigation of the origin of transferability have been considered for the stated class of chemical compounds.
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    International Journal of Quantum Chemistry 39 (1991), S. 59-70 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Simple net sign analysis has been carried out for particle in one- and two-dimensional boxes and harmonic oscillators. The conclusion that no simple rule for the ordering of eigenvalues of two-dimensional systems can be drawn is conjectured. Cyclobutadiene, naphthalene, benz-cyclobutadiene, biphenylene, biphenyl, and p-terphenyl are found to behave topologically as particle in either type of potential. Benzene, anthracene, naphthacene, and pentacene are found to behave topologically as particle in a two-dimensional harmonic oscillator. This analysis provides the physical basis for the net sign approach in the signed graph theory.
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    International Journal of Quantum Chemistry 39 (1991), S. 123-130 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We propose a fomula that directly gives an estimate of the value of a Gaussian integral through only one multiplication. Using this formula, we may neglect about 60%-80% of integrals in quantum chemical ab initio calculations, without any loss in precision theoretically. Such a large molecule as ATP with 183 STOS using the STO-2G method has been calculated utilizing this technique, and only 31 CPU hours of VAX 11/730 were spent on integrals.
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    International Journal of Quantum Chemistry 39 (1991), S. 163-172 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: A basis set of evenly spaced S-type Gaussian functions with common exponents is examined. Formulas for common one- and two-electron integrals are derived. Because of thesymmetry of this basis set, a very compact two-electron integral list is produced. The number of two-electron integrals that must be stored is approximately eight times the number of basis functions. Use of this basis set in an SCF calculation is examined. Numerical results show that this approach works well for molecules containing only small atoms such as hydrogen, helium, or lithium, but that the method has problems with the core orbitals of heavier atoms. Procedures for augementing this basis set in calculations involving heavier atoms are examined.
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    International Journal of Quantum Chemistry 39 (1991), S. 227-228 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    International Journal of Quantum Chemistry 39 (1991), S. 231-231 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Notes: The correlated, size-consistent, ab initio effective valence-shell dipole operator (μv) method is used to calculate dipole moments and transition dipole moments of the CH molecule and transition dipole moments of the CH+ ion as a function of internuclear distance. The dipole and transition dipole moments computed here compare well with those of other accurate ab initio methods. The transition dipole moments are then used to calculate oscillator strengths and radiative lifetimes for the A → X and B → A transitions of the CH+ ion and the A → X transition of the CH molecule. Comparisons are made with the best available theoretical and experimental lifetimes. Finally, the CH ground-state dipole moment function is used to evaluate overtone intensities and to examine simple models of the CH overtone intensities in polyatomic molecules.
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    International Journal of Quantum Chemistry 39 (1991), S. 299-308 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mulliken's model for the intensity of charge-transfer absorption bands in donor/acceptor complexes is extended to transition-metal compounds. Attention is focused on the analysis of systems containing a central metal ion and symmetrically equivalent π-acceptor ligands. The theory is illustrated for a one-donor/two-acceptor complex in D2d point symmetry. Results are stated for symmetries of commonly occurring transition-metal compounds that display well-documented metal-to-ligand charge-transfer transitions.
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    International Journal of Quantum Chemistry 39 (1991), S. 325-330 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: Drawing on the results of an analysis of the nature of the pulse that generates complete transfer of population from one to another level in a system with a discrete spectrum, a generalization of the method of stimulated emission pumping is proposed. It is shown that a small subset of the Fourier components of the optimal pulse will, if their relative amplitudes are the same as in the optimal pulse, generate almost as efficient a population transfer, thereby generating the opportunity to prepare a system in a selected state with a selected population.
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    International Journal of Quantum Chemistry 39 (1991), S. 309-324 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Model studies are reported aimed at accounting for the abrupt dependence of radiationless decay-rate constants on excess energy (known as channel-three decay in the case of S1 benzene) in singlet and triplet manifolds of benzene and azabenzenes. The favored model involves La(ππ*) state, strongly distorted along an out-of-plane coordinate, crossing the ground-state potential at an energy close to the minimum of the lowest excited state. The results are compared with experimental observations on benzene and three azabenzenes. Implications for photochemical reactions are also discussed.
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    International Journal of Quantum Chemistry 39 (1991), S. 353-370 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this paper, the density matrix formalism has been applied to treat ultrafast time-resolved absorption spectroscopy. We have shown that in the femto-second (fs) pump-probe experiments, the observed time-resolved absorption spectra consist of the contributions from the population (i.e., incoherent contribution) and the coherence (i.e., the phase of the system). The adiabatic approximation has been used to derive the expressions for ultrafast time-resolved spectra. We have also shown that the dynamics of the coherence will result in quantum beat. Numerical calculations have been performed to demonstrate the theoretical results.
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    International Journal of Quantum Chemistry 39 (1991), S. 411-422 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: C6H6 Raman scattering activities calculated from harmonic model ab initio Hartree-Fock 6-311 ++ G(d, p) polarizability derivatives (and harmonic force fields calculated at the same level) accurately simulate experiment (to within 1% for the a1g modes). Accurate predictions are also made for the e2g modes (to within 5% for ν7 and ν9, and more poorly for ν6 and ν8 [in Fermi resonance with ν6 + ν1]) and for the e1g out-of-plane mode, ν10. Only the ν6 in-plane CCC bending mode scattering activity is found to be anomalous. Systematic variation of the basis set indicates that the benzene scattering activities and depolarization ratios are strongly dependent on inclusion of both carbon and hydrogen atom diffuse functions in the basis set. Predictions are also made for 12C6D6 and for unmeasured intensities in 13C6H6. Measurements of a1g mode scattering activities in the latter molecule are predicted to be useful in testing the harmonic Hartree-Fock Raman intensity model.
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    International Journal of Quantum Chemistry 40 (1991), S. 347-360 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Any matrix can be expanded on a basis of SU(2) normalized irreducible tensorial matrices, NITM, defined in terms of 3-j symbols or coupling coefficients of SU(2). The NITM transform under rotations according to Wigner's matrices. If one dimension of an NITM is odd and the other even, the tensor has half-integer rank. A simple NITM basis consists of all NITM having the same numbers of rows and columns as the expanded matrix. A compound NITM basis consists of two or more simple bases, each spanning a corresponding block in the expanded matrix. The choice of NITM basis for expanding an effective Hamiltonian matrix is a crucial step in formulating a model. To illustrate the use of a compound NITM basis, including nonsquare NITM, an effective sp-type overlap-free superposition Hamiltonian is constructed and applied to the photoelectron ionization potential spectrum of water.
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    International Journal of Quantum Chemistry 40 (1991), S. 409-414 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In a recent work, Csvinszky formulated a variational density-functional approach for the investigation of the spatial generalization of Kato's theorem by March. In the previous work, a 10-electron model system (filled K and L shells) was considered. In the present work, the investigation is extended to two other cases: a 28-electron model system (filled K, L, and M shells) and a 60-electron model system (filled K, L, M, and N shells). As in the previous work, several expressions are adapted for the kinetic-energy functional of the electrons and the intriguing question of identifying the “best” kinetic-energy functional is raised and discussed.
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    International Journal of Quantum Chemistry 40 (1991), S. 421-428 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new type of correlation functional derived from the second-order expression for the correlation energy of an atom is proposed. The derived correlation potential contains one free parameter, which is determined by fitting the known pair correlation energy. The calculations with this potential in the Kohn-Sham approximation give rather accurate values for the matrix elements of different operators.
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    International Journal of Quantum Chemistry 40 (1991), S. 457-473 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown that the Heisenberg Lie algebra of the nondegenerate harmonic oscillator leads to a basis {J+, J0, J-} of LASU(2). The Hamiltonian of the system is proportional to J0, and the basis elements give rise to irreducible tensors in the associative enveloping algebra of the Heisenberg Lie algebra. The construction of these irreducible tensors is studied with special attention being paid to the case in which they act upon a single vector space spanned by the harmonic oscillator basis functions. A tensor coupling rule is developed, and useful application is made of it in the calculation of general expressions for vibrational operators and their matrix elements. Throughout, the value of the additional algebraic quantum numbers (l, m) is emphasized.
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    International Journal of Quantum Chemistry 40 (1991), S. 501-510 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In excited states of atoms and molecules, as well as in time-dependent situations, the one-electron density no longer suffices to completely characterize the electronic state; in addition, one now requires information about the electronic phase or the current density. We show that, for a stationary electronic state, the continuity equation of quantum fluid dynamics represents a differential equation for the electronic phase, which must be solved subject to certain periodicity conditions. These periodicity conditions arise from the nodal topology of the wave function and give rise to quantized vortices of current. The consequences of writing an electronic “wave function” for a many-electron system directly in terms of the single-particle density and phase have been investigated. We have shown that such a procedure leads to the appearance of an “internal magnetic vector potential.” We also establish the connection between the electronic phase and the geometrical (“Berry”) phase accompanying the adiabatic transport of a quantal system around a closed loop in parameter space. This leads to a generalization of the current density concept and allows us to discuss the geometrical phase in terms of the circulation of this current in parameter space.
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  • 62
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    Polymer Engineering and Science 31 (1991), S. 110-115 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A new crystallization kinetic equation has been derived considering the decrease in growth rate. The average linear growth rate of spherulite was assumed to be proportional to the m-th order of the uncrystallized fraction of the crystallizing material. A modified Avrami equation, 1 - Vc = exp[-Kf(t)n], was used where f(t) is the integral of the growth function, (1 - Vc)m. The validity of the equation was tested by analyzing the isothermal crystallization kinetic data of poly(ethylene terephthalate) from the melt using differential scanning calorimetry.
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  • 63
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    Polymer Engineering and Science 31 (1991), S. 99-103 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Process changes aimed at improving printer engine performance must take into consideration not only the process variables (such as nip temperature and pressure and process time to), but also the melt rheological variables (such as the characteristic time scale of the toner Tc). The melt rheology relevant to the electrophotographic toner fusing process is discussed. One criterion for toner quality can be conveniently measured through the Deborah number De, which is the ratio of Tc to to. Modification of the melt rheology by matrix polymer composition and carbon black size and concentration has previously been explored. Here, the melt rheology of toners with a range of gel content was studied using a step shear test. The coupled relaxation model was employed to fit the stress relaxation data. The viscoelastic properties were calculated from the melt data with this model. These properties were then used to estimate the strain deformation of the toner as it passes through the nip with arbitrary residence time and nip pressure as a function of gel content. This method can be used to match the toner melt properties with the processing conditions.
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    Polymer Engineering and Science 31 (1991) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 65
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    Polymer Engineering and Science 31 (1991), S. 125-139 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The unified numerical simulation of the filling/postfilling stages of the injection-molding process described in Part I is compared in the present paper with experimental results obtained with instrumented test molds. Flush-mounted pressure traces in the delivery system as well as in the cavity are favorably compared with corresponding predictions for both an amorphous and a semicrystalline polymer. It is demonstrated that the present unified formulation is well suited to handle complicated molds where compressibility effects can become important even during the filling stage, as portions of the cavity fill and undergo a packing behavior even when other regions of the cavity are still only partially filled.
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  • 66
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    Polymer Engineering and Science 31 (1991), S. 116-124 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This study employs a unified theoretical model to simulate the filling and postfilling stages of the injection-molding process. Implementation of such a model is based on a hybrid finite-element/finite-difference numerical solution of the generalized Hele-Shaw flow of a compressible viscous fluid under nonisothermal conditions. The shear viscosity of the polymeric material is represented by a Cross model for the shear-rate dependence and a WLF-type functional form for the temperature and pressure dependence, whereas the specific volume is modeled in terms of a double-domain Tait equation. The analysis also handles variable specific heat and thermal conductivity of the polymer as a function of temperature. Complex thin parts of variable thickness can be modeled and discretized by flat, triangular finite elements which may have arbitrary orientation in three-dimensional space, whereas runners and possible round pins or bosses in the part are represented as one-dimensional circular-tube elements. A control-volume scheme is employed that leads to automatic melt-front advancement during the cavity-filling stage.
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    Polymer Engineering and Science 31 (1991), S. 140-144 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The characteristic sigmoid compressive stress-strain relationships of sponges and their layered arrays are described by two kinds of mathematical models having three experimentally determined parameters. Since sponge compression is not accompanied by a significant cross-sectional area expansion, it was assumed that the stress in a multilayered array is the same in each layer. This enables prediction of the array's stress-strain relationship from the parameters of the individual layers and their known thickness. The applicability of the method is demonstrated with experimental data of two kinds of double-layered arrays of polyurethane sponges. It is shown that the arrays' compressive behavior can be satisfactorily predicted irrespective of the mathematical form of the model and whether the strain is expressed as engineering strain or Hencky's.
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    Polymer Engineering and Science 31 (1991), S. 145-152 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The gapwise density distributions of the injection molded specimens of two engineering thermoplastics, i.e., poly(phenylene ether) and poly(ether imide), were characterized employing the density gradient column technique. The samples were molded using a 40t Van Dorn injection molding machine. The effects of the thermal history on the density distribution of unconstrained quenched specimens were also investigated. In addition, various material properties, such as pressure-volume-temperature, isothermal contraction, and pressure induced densification behavior were characterized, for the two resins employed in this study. The moldings of the two resins exhibited different trends in their density distributions. These findings were explained in terms of the competing effects of cooling rate and the pressure history experienced by the engineering plastic resins during the molding cycle. The data collected were also used as input to mathematical modeling of density distributions in injection molded articles, which is reported in Part II of this article.
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    Polymer Engineering and Science 31 (1991), S. 191-196 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The problem of steady solidification of a power law fluid flowing in a round tube was solved numerically. The fluid considered was a polymer with temperature dependent viscosity. The mathematical solution was obtained by using an implicit finite difference method. Results are presented to show the effects of the Peclet number, Nahme number, and the power law index on the profiles of the frozen layer. Melt temperature profiles at different axial locations are also presented.
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    Polymer Engineering and Science 31 (1991) 
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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    Polymer Engineering and Science 31 (1991), S. 197-203 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Extensional flow of a bicomponent two-layer slot cast coextrusion process has been studied. A Newtonian and an upper-convected Maxwell fluid were considered to be the two layers, respectively, and the two-layer flow was assumed to be steady and isothermal. This choice was made as a simple model for a system which consists of two distinctly different fluids in terms of their extensional behaviors. Present study considered only the draw-down region where the film thickness changes slowly with the distance from the die exit. For this region, asymptotic solutions could be obtained for two limiting cases in which the elasticity effect of the Maxwell fluid layer is small and the applied tension at the take-off is large, respectively. When the elasticity effect is small, the melt thickness and the velocity profiles are exponential as in the case of a Newtonian single-layer flow. When the applied tension is large, on the other hand, the velocity profile is shown to be near linear. Furthermore, the viscoelasticity effect of the Maxwell fluid layer becomes so dominant that it dictates the mechanics of the coextrusion flow even when its flow rate and shear viscosity may be much smaller than those of the Newtonian layer.
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    Polymer Engineering and Science 31 (1991) 
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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    Polymer Engineering and Science 31 (1991), S. 353-364 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Optimal open loop control strategies are developed for a semibatch free radical copolymerization of methyl methacrylate and vinyl acetate using the multiobjective dynamic optimization method. A detailed kinetic model is validated through experimentation and used for the design of optimal controls. Both monomer feed rate and reactor temperature are varied to produce the copolymer of desired composition and molecular weight. The open loop control policies are implemented in a process control computer and tested on an experimental stirred tank polymerization system. Excellent agreement between the model predictions and the experimental data have been obtained.
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    Polymer Engineering and Science 31 (1991), S. 333-352 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The dynamic behavior of two continuous stirred tank reactors in series has been investigated for free radical solution polymerization of styrene with a binary mixture of two initiators having different thermal decomposition activities. For a wide range of initiator feed composition, both reactors exhibit quite complex nonlinear steady state and transient behavior. When the reactor residence time is used as a bifurcation parameter, the second reactor can have up to five steady states. For certain range of reactor operating conditions, bifurcations to various types of periodic solutions have been observed, such as Hopf bifurcation, isolas, period doubling, period-doubling cascade, and homoclinics. The effects of other reactor variables, such as total initiator concentration, coolant temperature, and reactor volume ratio on the reactor dynamics, are illustrated to show the complex dynamic behavior of the two-reactor system catalyzed by a mixture of t-butyl perbenzoate and benzoyl peroxide.
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    Polymer Engineering and Science 31 (1991), S. 365-375 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This paper presents the development of a novel in-line extrusion rheometer based on the flow of polymer through a wedge (vertically tapered slit). This rheometer is suitable for measuring changes in rheological properties on-line during reactive extrusion, because it can be used to estimate the viscosity for a range of shear rates without the need to change the polymer flow rate (i.e., extruder throughput). Equations have been developed to estimate the parameters of the power-law equation, used to describe the viscosity-shear rate relationship, from measurements of pressure drops along the wedge. An experimental in-line wedge rheometer has been built and used to measure the viscosity for a series of polypropylenes prepared via reactive extrusion. Viscosity measurements from the experimental in-line wedge rheometer are compared with measurements from a capillary rheometer. Good agreement is found between the capillary and wedge rheometer measurements.
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    Polymer Engineering and Science 31 (1991), S. 391-391 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 77
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    Polymer Engineering and Science 34 (1994), S. 6-11 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A new class of materials based on a spirodilactam structure has been recently synthesized as part of research into new polymeric materials. Not only is the spirodilactam structure novel, but it was not even the intended product in the synthesis as originally designed. The polymerization process discovered by the reaction of 4-ketopimelic acid or its corresponding spirodilactone with primary amines opened a new field of polysprodilactam chemistry. This paper describes the chemistry leading to the discovery of spirodilactam-based polymers and initial applications in the area of thermoplastics and thermosets. Most recent developments to be covered include aromatic spirodilactams and isomeric spirodilactams.
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    Polymer Engineering and Science 34 (1994), S. 12-16 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Spirodilactam bisallylether is a new high temperature performance monomer. It melts at 154°C, and is thermally inactive in forming a homopolymer. However, it reacts readily with a bismaleimide via “ene” reaction. Therefore, it could be used as a comonomer and an effective toughening modifier for bismaleimide. The properties of the blends of spirodilactam bisallylether and 4,4'-bismaleimidodiphenyl-methane were studied. The cocured resins have high glass transition temperature, 〉 300°C. By adding 30 to 40 mole % of the bisallylether, the compact tension toughness of the bismaleimide was improved to 0.7 MPa-m1/2. Therefore, the resins have a combination of high glass transition temperature and toughness. They also showed good flexural properties. Despite the high water absorption, 5 to 7%, the resins retained high hot/wet flexural properties because of the high glass transition.
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    Polymer Engineering and Science 34 (1994), S. 59-68 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Four immiscible blend systems, styrene-maleic anhydride/styrene-acrylonitrile (SMA/SAN). styrene-maleic anhydride/acrylonitrile-butadiene-styrene (SMA/ABS), poly(vinylidene fluoride)/SAN (PVF2/SAN), and PVF2/ABS, were investigated. The effect of adding up to about 10 wt% of a third polymer that is miscible with each blend component, poly(methylmethacrylate) (PMMA), was determined. In every case, the addition of PMMA led to the improvement of properties such as tensile strength, tensile elongation, and notched impact strength. Furthermore, the addition of PMMA resulted in finer, more uniform dispersions of the primary blend components. The experimental results are interpreted in terms of interfacial activity of the common phase component, PMMA.
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    Polymer Engineering and Science 34 (1994), S. 81-85 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Differential scanning calorimetry (DSC) was used to investigate the solid-state cure process of poly(phenylene sulfide)(PPS) resin. Virgin PPS resin in an open sample pan was cured in DSC cell. Either air or oxygen was used as a curing atmosphere. Cure temperatures were in the range of 200 and 250 °C, which are below the melting point of PPS resin. Cure temperature as well as atmospheric condition influenced the cure behavior of PPS in the solid state. Both the rate and the amount of cure increased with increasing cure temperature. On the other hand, the time to reach the maximum cure rate was independent of cure temperature. Changing the atmosphere from air to oxygen increased both the cure rate and the amount of cure. The size effect of PPS particles on the cure reaction was also discussed.
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    Polymer Engineering and Science 34 (1994), S. 109-115 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Slow crack growth was measured in the perpendicular and parallel directions relative to the extrusion direction of the pipe. For five pipes from different manufacturers, the anisotropy factor, the lifetime to fracture in the perpendicular direction divided by lifetime in the parallel direction, varied from 1.2 to 4.7 for complete fracture and 1.4 to 4.0 for crack initiation. The degree of molecular orientation was determined by measuring the shrinkage that occured when a pipe specimen was heated near its melting point. The amount of shrinkage correlated with the anisotropy factor for slow crack growth. The shape change after shrinkage was related to the flow pattern of the resin during extrusion and the cooling rate after extrusion.
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    Polymer Engineering and Science 34 (1994), S. 135-140 
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The complex Young's modulus, E*(ω), and the complex strain-optical coefficient, O*(ω), of poly(ether sulfone) (PES), polysulfone (PSF), and polyethermide (PEI), were measured over the frequency range 1 to 130 Hz. The data were analyzed with a modified stress-optical rule: The Young's modulus was decomposed into two complex functions, EG*(ω) and ER*(ω); the modified stress-optical coefficient, CR and CG, associated with the rubber (R) and glass (G) components, respectively, were determined. The results for six polymers, including polystyrene, poly(α-methyl styrene), and bisphenol A polycarbonate were compared with each other. One of the coefficients, CR, equivalent to the stress-optical coefficient in melts, mainly depended on the way in which phenyl groups were connected to the chain. The other, CG, was in the range of 20 to 40 Brewsters, and did not strongly depend on the details of polymer structure. The component function, EG*(ω), which was located in the glassy region and originated from the high glassy modulus, was almost the same in shape when plotted against ω with double logarithmic scales. The R component, ER*(ω), located at the long time end of the glass-to-rubber transition zone, was slightly sensitive to the molecular structure of polymers.
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    Polymer Engineering and Science 34 (1994), S. 159-165 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: While there is abundant evidence that the molecular weight distribution (MWD) of a linear polymer has an influence on the shape of the viscosity function, the ability to convert the viscosity function to an MWD has been questioned. Using strictly numerical techniques, we have shown that the viscosity function can be transformed to the MWD, but always with some distortion. However, distinct bimodality can be qualitatively preserved through both the MWD-viscosity and viscocity-MWD transforms.
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    Polymer Engineering and Science 34 (1994), S. 169-173 
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    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In microcellular plastics, an unfoamed skin that is integral with the foamed core can be created by allowing the nucleating gas to diffuse from the surfaces of a gas saturated specimen prior to foaming. In this paper, a semi-empirical model is proposed that predicts the skin thickness variation in microcellular foams as a function of gas desorption time. The model shows good agreement with experimental results on the polycarbonate-carbon dioxide system.
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    Polymer Engineering and Science 34 (1994), S. 174-189 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The present paper proposes “Deformation Characteristics” (DC) as a new deformation measure of screw extrusion processes, based on the Green deformation tensor. In contrast to previous strain measures heuristically proposed by Mohr, et al., Mckelvey, and Pinto and Tadmor, the new DC can naturally incorporate the demixing phenomena and systematically take into account the three-dimensional circulatory flow with the screw flight effect. Therefore, DC can be regarded as an improved strain measure. “Weighted Average Deformation characteristics” (WADC) is also proposed to indicate the overall deformation characteristics as a quantitative measure to the “goodness of mixing” of the extrusion process. The present paper includes discussion on delicate differences between DC and several other strain measures in case of the two-dimensional velocity approximation, and on the application of DC into a general three-dimensional velocity field obtained by a quasi-three-dimensional finite element analysis of extrusion processes. In determining WADC in the three-dimensional application, the residence time distribution function, including the three-dimensional circulatory flow effect, is used.
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    Polymer Engineering and Science 34 (1994), S. 229-237 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Non-isothermal flow is simulated in the screw and kneading disc elements in a modular co-rotating twin screw extruder. Methods of calculating mean temperature rises for individual elements are discussed and results are presented. The implications of non-isothermal operation for scale-up is discussed. A method is then described for making calculations in a modular co-rotating machine, that contains many different elements. Example calculations are given showing the tendency of larger machines to buildup greater temperatures when viscous heating is included.
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    Polymer Engineering and Science 34 (1994), S. 221-228 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A study of the influence of a compatibilizing agent on phase morphology development in a 75/25 polyethylene/polyamide-6 blend in a modular co-rotating twin screw extruder is presented. The development of phase morphology along the axis of the modular screw was observed by cooling the extruder and removing the polymer from the screw channels. Changes in phase morphology due to the addition of a compatibilizer have been investigated using scanning electron microscopy. Sufficient quantities of compatibilizing agent produce significant increases in the rate of mixing and also reduce the scale of the phase morphology. Much larger quantities (5%) than actually required for interface coverage are needed for rapid mixing. This seems to be due to the high viscosity of the matrix.
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 251-251 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 89
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 90
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 260-265 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Penrose states that quantum effects can occur even in relatively large systems when energy differences remain small. This is just the situation with polymer materials. A quantum description by Penrose of the formation of quasi-crystals can be rewritten to apply to polymer crystallization. The implications of the need to take account of quantum effects are discussed. Another approach based on the quantization of energy levels in clusters of atoms offers a possible explanation of heat setting in nylon and polyester fibers. Finally some problems of the interpretation of quantum theory are discussed.
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  • 91
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A novel approach to a truly dynamic thermodynamics is proposed in which equilibrium is defined in terms of explicit time, distance, and acceptable error scales. This approach involves reformulating the second law of thermodynamics in terms of an excess energy that vanishes at equilibrium instead of an entropy that assumes some unknown maximum value. Excess energy is defined mathematically as the total Legendre transform of energy with respect to an independent set of extensive variables. Excess energy is effectively the free energy functional of a nonequilibrium system and is a function of the time, distance, and acceptable error scales. Elimination of entropy from thermodynamics requires recognizing temperature as a thermal stress, proportional to the antimetric component of the stress tensor that is neglected when one assumes the validity of Cauchy's second law of motion. The inclusion of temperature as part of the stress-strain couple completes the science of thermomechanics and opens the way for a practical unification of chemistry and physics in strictly mechanical terms.The last sentence of the abstract shows how high the goals that Lindem meyer set for himself were. I personally do not agree with the idea that mechanics is the queen of all sciences, and that given deep enough probing one could achieve “a practical unification of chemistxy and physics in strictly mechanical terms”; for instance, electromagnetism has full citizenship's rights in physics, and it is hard to conceive that it could be reduced to mechanics.
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  • 92
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The interfacial strength of two paper-polypropylene-paper laminates used for electrical power transmission cable insulation has been measured using a peel test after a variety of conditionings that simulate the service thermal stress conditions. Immersion in dielectric oil at 23°C causes little decrease in peel strength, but heating in the oil at 90°C causes a rapid initial loss followed by a slow loss of strength. Cyclic and static heating show that cyclic fatigue is not a factor as the initial loss of strength occurs in a time comparable to the first two test cycles and further heating causes much less loss of strength. Tensile and compressive stresses resulting from cable winding have no effect on the loss of bond strength during heating in oil. Vacuum drying of the laminate and oil (as in cable manufacture) before heating results in less decrease in peel strength than heating without prior drying. Optical and electron microscopy show minimal wetting of the paper fibrils by the polypropylene with only a few having been either normal to or at a steep angle to the polypropylene surface. That is, the fibrils appear to be parallel to the interface and only partially immersed in the polypropylene. Micrographs show little, if any, differences between the interfaces on the two sides as well as little paper on the polypropylene after delamination and vice versa. It is suggested that the bonding mechanism is a combination of weak mechanical interlocking and secondary bonds. It is also suggested that swelling of the polypropylene relative to the paper by the dielectric oil at 90°C weakens the interfacial bond.
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  • 93
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 290-300 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Variations of stress with temperature for stretched networks of trans-polyisoprene networks in the crystallization region are reported. Such profiles are characteristically U-shaped with the stress at lower temperatures often climbing to high levels. Valley widths of the profiles narrow as annealing temperature increases to about 50°C, then widen at yet higher temperatures. The degree of crystallization at 22°C is 37% and independent of deformation and annealing temperature. The β crystal form is overwhelmingly present with traces of other crystal forms appearing only at high deformations. The theory of stress-induced crystallization provides a good description of experimental results provided the nucleation parameter σ is dependent upon deformation. Therefore, the data provide good qualitative support for the theory in its current form.
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  • 94
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polyalkylenebenzoxazoles of high molecular weight (inherent viscosity values from 0.76 to 2.95) were prepared from 4,6-diaminoresorcinol dihydrochloride and aliphatic diacids in polyphosphoric acid by heating at 180 to 200°C for 3-5 h. Melting points of the polymers ranged from 148 to 423°C, depending on the length of the alkylene chain. Glass transition temperatures were relatively low, ranging from 50 to 100°C and did not show the pronounced odd/even effect noted for melting points. In all cases, rapid weight loss occurred above 400°C. No evidence for the formation of a molecular composite was observed in an attempt to prepare in situ a rod-like polybenzoxazole in a polyalkylenebenzoxazole.
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  • 95
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 96
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 93-101 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Low levels of oligomer molecules are generally desirable in polymeric materials. It is known that several reactor variables can affect the oligomer distribution, and therefore it is useful to have predictive models for molecular weight distribution. The normal approach of a differential equation-based model is very complex to set up if it is applied rigorously to include all the non-Flory aspects of the step growth polycondensation and in particular the interfacial polycarbonate polymerization. In this paper, simple methods based on the Monte Carlo method and Stockmayer distribution are applied to simulate the effects of mass-transfer, unequal reactivity, and the starting stoichiometry of the polycondensing functional groups on the oligomer distribution. It is shown that these parameters can have a significant effect on the oligomer weight distribution and polydispersity of the final polymer.
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  • 97
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 308-317 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The true crystallite modulus of polyoxymethylene (POM) was evaluated experimentally and thoeretically as a function of temperature. The mechanical deformation mechanism of POM was lattice-dynamically predicted and confirmed by measuring the stress-induced vibrational frequency shifts of the infrared and Raman spectra, which were interpreted on the basis of anharmonic potential field.
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  • 98
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 141-152 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The ultra-high strength/modulus, extended chain polyethylene fiber (Spectra® fiber) composite has shown great potential as a lightweight armor material with its extraordinary capability of absorbing the kinetic energy of projectiles. But the relatively low melting point of this fiber (∼ 145°C) has caused concerns regarding the effect of temperature rise during the impact/penetration process on the performance as armor material. In this article, an analysis of temperature rise in projectile and the fiber composite during the impact/penetration process is described. Combining the simulation of impact deformation by finite element analysis and the simulation of temperature rise by a finite difference approximation of the related dynamic equations, the temperature rise caused by the projectile/composite interaction was estimated. Results show that there is a significant temperature rise at the projectile/composite interface due to the friction but that the short length of time involved in the process and the low thermal conductivity of Spectra fiber composite keep the temperature rise in a very small region (in the order of 0.001 cm) around the interface during the impact/penetration process. Consequently, the volume that is affected by the temperature rise is very small, in the order of total 0.001 cm3 around the projectile, and this is too small to generate any detectable effect on the armor performance. After the projectile is stopped, however, substantial heating of fiber composite can occur under specific conditions as the result of heat flow from the hot projectile embedded in the composite. This heating of fibers, however, is a postmortem effect and hence inconsequential to the ballistic performance of the composite armor.
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  • 99
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 100
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 190-200 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A mathematical model of a polycondensation reactor that can be used in the final stage for poly(ethylene terephthalate) (PET) is established and compared with experimental data obtained from a laboratory scale reactor with film renewal. Detailed side reactions are considered along with the diffusional removal of the small molecules through thin film. Among several kinetic constants, the polycondensation reaction rate constant k1(= k8) and diester group degradation reaction rate constant k7 have an influence over the degree of polymerization. The values of k1(= k8) and k7 for 0.05 wt% Sb2O3 were obtained as curve-fit values: (1) k1(= k8) = 3.4 × 106 exp(- 18.500/RT′) (L/mol-min); (2) k7 = 1.3 × 1011 exp(- 37,800/RT′) (min-1). Effects of the film exposure time, reduced pressure of vacuum, temperature, the initial terephthalic acid (TPA)/ethylene glycol (EG) mole ratio, the initial degree of polymerization, and catalysts were well explained by the model.
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