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  • American Institute of Physics (AIP)  (26.481)
  • International Union of Crystallography (IUCr)
  • 2000-2004  (30.797)
  • 1970-1974  (4.538)
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  • 1
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 7621-7626 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: When placed into an external magnetic field inhomogeneous porous structures, like rocks, cement gels, ceramics, etc., exhibit strong local magnetic field gradients (LMFG), which are inherently related with the size, shape, and distribution of their pores. In this paper, we present a method of measuring LMFG in a liquid-filled porous media, provided that the fast exchange model sufficiently describes water motion in the pores, which is based solely on the measurement of the water 1H NMR spin lattice relaxation rates and the knowledge of the unrestricted diffusion coefficient. The method is applied to two hydrating white cement samples with different hydration kinetics, and the results are correlated with the time evolution of the pore structure. It is shown that the measured LMFG have extremely high values, which qualitatively reflect the sharp needlelike morphology of the internal cement gel surface. © 2000 American Institute of Physics.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 7627-7634 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: By use of optical steady state and time resolved spectroscopy, we studied the evolution of the triplet excited state in a series of six ethynylenic polymers of the structure [-Pt(PBu3n)2-C(Triple Bond)C-R-C(Triple Bond)C-]n where the spacer unit R is systematically varied to give optical gaps from 1.7–3.0 eV. The inclusion of platinum in the polymer backbone induces a strong spin-orbit coupling such that triplet state emission (phosphorescence) associated with the conjugated system can be detected. Throughout the series we find the S1-T1 (singlet-triplet) energy splitting to be independent of the spacer R, such that the T1 state is always 0.7±0.1 eV below the S1 state. With decreasing optical gap, the intensity and lifetime of the triplet state emission were seen to reduce in accordance with the energy gap law. © 2000 American Institute of Physics.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 7511-7518 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A modified conductorlike screening continuum solvation model, implemented in the quantum chemistry program GAMESS, has been extended to second order perturbation theory (MP2). Two possible schemes have been considered: (a) the calculation of the MP2 energy using the solvated Hartree–Fock (HF) orbitals, and (b) the implementation of a double-iterative procedure where the HF density is updated with respect to the MP2 surface charges. The influence of the self-consistency of the surface charge distribution with respect to the MP2 density has been analyzed for a small dataset of 21 neutral molecules and 13 ions. In addition, the details of the distribution of surface charge density (σ profiles) and the effects of electron correlation on the accuracy of such distributions is analyzed in terms of the overall concept of deviation of continuum models from dielectric theory, leading to insights into higher order models. © 2000 American Institute of Physics.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 4
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 7519-7529 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The conductorlike continuum solvation model, modified for ab initio in the quantum chemistry program GAMESS, implemented at the Møller–Plesset Order 2 (MP2) level of theory has been applied to a group of push–pull pyrrole systems to illustrate the effects of donor/acceptor and solvation on the stability and energetics of such systems. The most accurate theoretical gas and solution phase data to date has been presented for the parent furan-2-carbaldehyde (furfural) system, and predictions made for three additional analogues, thiophene-2-carbaldehyde, pyrrole2-carbaldehyde, and, cyclopentadiene-1-carbaldehyde. Solvent effects on internal rotational barriers in all systems were evaluated over six different values of dielectric, using the new method. Calculated electrostatic energies are shown to be highly sensitive to level of theory incorporated. © 2000 American Institute of Physics.
    Materialart: Digitale Medien
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  • 5
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 7554-7563 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Exploiting an electrostatic analogy, we show that the elastic forces between a set of rigid particles embedded in a phantom polymer network can be represented by a simple bead-and-spring model. The beads represent the particles and the springs the rubber matrix. The model is validated by Monte Carlo simulation of rubbers filled with hard spherical particles, at volume fractions between 0.1 and 0.3. We derive both the moduli and the full stress–strain curves, under uniaxial elongation. The model reproduces and extends previous theoretical results on the so-called hydrodynamic reinforcement effect. © 2000 American Institute of Physics.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 7571-7577 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The temperature dependence of electron transmission through various organized organic thin films (OOTFs) was investigated. For most systems a strong dependence of the transmission efficiency on temperature was observed, even for a relatively small temperature range. The well defined structure of the OOTFs and the monitoring of the angular dependence of both the initial and the final velocities of photoelectrons were used to reveal the mechanism behind the temperature effect and further elucidate the transmission mechanism. A simple model, which assumes that the electron transmission yield is much higher along the organic chains than in any other direction, was able to reproduce the experimental observations. We find that the photoelectron transmission yield through OOTFs is extremely sensitive to the structural order in the film. © 2000 American Institute of Physics.
    Materialart: Digitale Medien
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  • 7
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 7546-7553 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Femtosecond vibrational wave-packet dynamics in a cyanine molecule is observed to be strongly dependent on the chirp direction of the excitation pulse. The slow-decay component associated with an oscillatory structure, which corresponds to the excited-state lifetime and a vibrational mode of 160±10 cm−1, respectively, is measured by the femtosecond time-resolved transmission spectroscopy. The excited-state population is substantially decreased and enhanced in the cases of negatively chirped (NC) and positively chirped (PC) excitations, respectively. A quantum mechanical calculation by means of the split operator scheme is performed to reproduce the wave-packet propagation after the chirped pulse excitation. The calculation shows that the spatial distribution of the wave packet for the NC case is narrower than that for the PC case during the excitation, and that the overlap integral between the excited- and ground-state wave packets determines the efficiency of the population dumping. © 2000 American Institute of Physics.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 7564-7570 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Metastable impact electron spectroscopy (MIES) and ultraviolet photoelectron spectroscopy are used in this study to investigate low-defect and defective MgO(100) thin films. Unlike low-defect films, defective films exhibit a new spectroscopic feature located ∼2 eV above the top of valence band. Exposing the defective film to oxygen quenches the emission of electrons from F centers created on the surface and in the subsurface regions. Extended defects, unseen in the MIES spectra of the clean surface, are detectable using NO titration. MIES and thermal programmed desorption indicate that at ∼100 K NO adsorbs dissociatively on defects, forming N2O. Only a small fraction of the MgO surface becomes covered with N2O at ∼100 K for the low-defect MgO film indicating that N2O molecules preferentially adsorb on the extended defects. The saturation coverage of N2O increases appreciably for the defective sample. © 2000 American Institute of Physics.
    Materialart: Digitale Medien
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  • 9
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 7530-7545 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The Yang–Yang relation expresses the heat capacity at constant volume, CV(T,ρ), of a fluid linearly in terms of the second temperature derivatives of the pressure and the chemical potential, p″(T,ρ) and μ″(T,ρ). At a gas–liquid critical point CV diverges so, on approaching Tc from below, either pσ″(T), or μσ″(T), or both must diverge, where the subscript σ denotes the evaluation of p and μ on the phase boundary or vapor-pressure curve. However, previous theoretical and experimental studies have suggested that μσ″(T) always remains finite. To test these inferences, we present an analysis of extensive two-phase heat capacity data for propane recently published by Abdulagatov and co-workers. By careful interpolation in temperature and subsequently making linear, isothermal fits vs specific volume and vs density, we establish that the divergence is shared almost equally between the derivatives pσ″(T) and μσ″(T). A re-examination of the analysis of Gaddy and White for carbon dioxide leads to similar conclusions although the singular contribution from μσ″(T) is found to be of opposite sign and probably somewhat smaller than in propane. © 2000 American Institute of Physics.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 7578-7581 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Circular-difference effects in second-harmonic generation have been used to study chiral, anisotropic thin films of a helicene derivative. For such samples, these effects arise both from the chirality of the film and from its anisotropy. We show theoretically and experimentally that there is a fundamental difference between a circular-difference effect originating from chirality and anisotropy. A method is described that distinguishes the two contributions. © 2000 American Institute of Physics.
    Materialart: Digitale Medien
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