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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 27 (1985), S. 145-157 
    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 orthogonalized direct diagonalization (ODD) method is used to predict the valence-shell ionization spectra for the series of hydrocarbons ethane (C2H6), ethylene (C2H4), and acetylene (C2H2) within an EOM/propagator formalism. Both (a) third-order and (b) higher-order (with h5 terms in the excitation operator manifold) calculations are presented in order to illustrate the effect of the extended operator manifold on the predicted valence-shell spectra. It is shown that the major effect of the h5 manifold is concentrated in its “occupied” part. Along with a general shifting of the main lines for outer valence ionizations to lower values (together with a slight reduction in pole strength), it is found that the effect of the h5 manifold in the inner valence region is dependent on the system being studied.
    Additional Material: 3 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 43 (1992), S. 327-342 
    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 local origin/local orbital (LORG) method of Hansen and Bouman has been implemented with the intermediate neglect of differential overlap Hamiltonian for spectroscopy (INDO/S). The method is shown capable of demonstrating the inductive effects associated with electron-withdrawing substituents through the diamagnetic shielding term. In addition, the method is capable of differentiating chemical shift in differing bond environments. The calculated paramagnetic contribution, however, is deficient for substituents that saturate the minimal basis such as oxygen and fluorine, which severely limits the general utility of the procedure. Through the utilization of reduced linear equations for the paramagnetic term, the method is amenable to any molecule for which a self-consistent field can be performed and therefore can potentially be used to study very large systems. At present, however, the LORG method when used with the rapid INDO/S model Hamiltonian does not reliably reproduce the paramagnetic contribution to the shielding.
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 56 (1995), S. 733-746 
    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: Density functional theory (DFT) was used to study reactions involving small molecules. Relative energies of isomers and transition structures of diazene, formaldehyde, and methylenimine were determined using various DFT functionals and results were compared with MP2 and MP4 calculations. DFT reaction barriers were found to be consistently lower. For some reactions, such as OH + H2→ H2O + H, gradient-corrected functionals predict very low or nonexistent barriers. The hybrid Hartree-Fock-DFT adiabatic connection method (ACM) often provides much better results in such cases. The performance of several density functionals, including ACM, was tested in calculations on over 100 atomization, hydrogenation, bond dissociation, and isodesmic reactions. The ACM functional provides consistently better geometries and reaction energetics than does any other functional studied. In cases where both HF and gradient-corrected DFT methods underestimate bond distances, the ACM geometries may be inferior to those predicted by gradient-corrected DFT methods. © 1995 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 4 (1970), S. 431-450 
    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 one-centre CI wave function for HeH+ reported by Stuart and Matsen for 0.1 ≤ R ≤ 5.0 has been analysed in detail from the viewpoint of molecular formation. Further, by means of a natural orbital analysis, it was possible to obtain some measure of the electron correlation contained within such wave functions for various R values. These effects were illustrated by means of a series of difference maps for the electron density. One- and two-particle expectation values were obtained as a function of R. Thus, it was possible to study several aspects of the influence of the proton on the electron charge cloud as we pass from He through to the united atom Li+. The occupation numbers within the natural expansions were compared with those which arise from a similar analysis of a two-centre wave function for HeH+. The “character” of such wave functions for HeH+, and also for He and Li+, were analysed and compared.
    Additional Material: 5 Ill.
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  • 5
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acrylonitrile (AN) was graft-polymerized onto gelatinized cationic starch (CS) possessing diethylaminoethyl ether groups by cerium (IV) initiation to give stable latexlike copolymer dispersions. Dispersions of the latex copolymers, having up to 50% grafted polyacrylonitrile (PAN), air- and heat-dry on glass to clear, adhesive films. Sonification of up to 8% dispersions at 20 Khz reduced their viscosities from 1500-3000 cP to 15-40 cP. Scanning electron microscopy revealed that both nonsonified and sonified dispersions consist of ball-like particles measuring about 0.05-0.15 μ in diameter when dry. The films are formed by coalescence of these particles. The degree to which AN grafts onto CS at ambient temperature is related to the nitrogen content of CS, gelatinization time of CS at 95°C, sequence of AN and cerium(IV) addition, concentration of cerium (IV), concentration of AN, and severity of reaction agitation. Number-average molecular weight values of PAN were about 106 when grafting was conducted under stirring and about 5 × 105 when conducted under shaking action.
    Additional Material: 3 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 23 (1985), S. 1555-1562 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The wetting characteristics of free-standing polyacetylene films were determined by using a standard series of wetting liquids. As-prepared films of cis-polyacetylene were found to contain a significant polar contribution to the surface free energy, which became nearly entirely dispersive upon thermal isomerization to the trans form. Both isomeric forms are characterized by a critical surface tension of wetting γc ≈ 51 mN/m, which is considerably higher than that normally obtained from organic polymers. These results have been interpreted with respect to surface oxidation and tested by examining an oxidized film.
    Additional Material: 3 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 1041-1054 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray diffraction scans and infrared absorption spectra for the C-CI stretching region were obtained for a highly syndiotactic poly(vinyl chloride) (PVC) sample made by the urea clathrate method. When the polymer was annealed at a series of increasing temperatures up to 180°C, x-ray diffraction measurements showed that the crystallinity increases steadily with annealing temperature. Even at 50°C an increase above the original value of 63% was detectable and by 180°C it had reached 70% with a further increase to 78% after cooling to ambient temperature. There is a concurrent significant increase in the lateral crystallite dimensions. However, the infrared spectrum did not change, in agreement with the recent prediction of Moore and Krimm that there is no observable band splitting from interchain interaction in crystalline regions, thus indicating that these C-CI bands cannot be used as a measure of crystallinity. The results from computer curve fitting of the spectra suggest that at least 85% of the polymer consists of long planar syndiotactic sequences and there is therefore substantial order along the chain direction. A mechanism for the increase in crystallinity on annealing, involving the lateral ordering of these regular chains, is discussed. Furthermore, as the temperature is raised some amorphous material is converted to a nematic phase, and this may crystallize during the subsequent cooling.
    Additional Material: 4 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2787-2793 
    ISSN: 0887-6266
    Keywords: gel ; arborol ; dendrimer ; freeze-fracture electron microscopy ; small-angle X-ray scattering ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reversible gels of two-directional cascade polymers with hydrophilic groups covalently attached by an hydrophobic center chain were studied by light and small-angle X-ray scattering, differential scanning calorimetry, and freeze-fracture transmission electron microscopy. The long, self-assembled fibers interact side-by-side over extended regions to form bundles. A given fiber may participate in several bundles, thus forming a three-dimensional gel network. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2787-2793, 1997
    Additional Material: 8 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 959-968 
    ISSN: 0887-6266
    Keywords: PTMSP ; cross-linking ; membranes ; permeability ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cross-linkable poly[1-(trimethylsilyl)-1-propyne] (PTMSP) films were cast from toluene solutions containing PTMSP and either 4,4′-diazidobenzophenone or 4,4′-(hexafluoroisopropylidene)diphenyl azide. The composite films were clear and homogeneous and were cross-linked by UV irradiation at room temperature or thermal annealing at 180°C. Low levels of the bis(aryl azide) (1-5 wt %) were effective in rendering the films insoluble in toluene and THF, both good solvents for PTMSP. The process is simple and effective, and thus PTMSP can be readily converted to mechanically stable membranes with permeabilities and separation factors comparable or higher than those of poly(dimethylsiloxane). The films were characterized by measuring their density, their permeability toward O2 and N2, and their spectroscopic properties. Compared to PTMSP, films containing bis(aryl azide) cross-linkers had lower permeabilities and higher separation factors, consistent with a reduction in free volume. When the films were cross-linked photochemically, the permeabilities declined further and the separation factor increased. Films cross-linked thermally had permeabilities comparable to their PTMSP/azide precursors, and density and swelling measurements suggest that higher free volumes are obtained in thermally cross-linked films. All films stored in air suffered from a slow decline in permeability which may reflect slow surface oxidation of the films. When stored in vacuum, cross-linked films were stable and showed no loss in permeability, but the permeability of uncross-linked PTMSP films stored under the same conditions fell to 70% of their original value in 1 month. We attribute the permeability decline to densification accelerated by impurities and solvents. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 959-968, 1998
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 40 (1991), S. 557-568 
    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 study of the electronic structure and spectroscopy of models of C60 and C70 cage structures has been carried out using the intermediate neglect of differential overlap (INDO) model Hamiltonian. The geometry for these cages was obtained using gradient-driven methods, and at least in the case of C60, where information is available, is in good accord with the calculations of others. Using a small active space of only single excitations, both configuration interaction (CI) and random phase approximations (RPA) yield spectra in excellent agreement with that obtained from recent experiments. The oscillator strength of the band calculated at ∼47000 cm-1, however, dramatically diminishes as the active space is increased, even though the sum rule increases. We discuss this interesting observation as well as the calculated structure and spectrum of C70.
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