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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 6411-6420 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Nuclear magnetic relaxation caused by self-diffusion induced modulation of the intramolecular nuclear interactions in nematic liquid crystal droplets embedded in a solid polymer matrix is analyzed in order to show when it allows the determination of the structure of such confined systems. Both the frequency and temperature dependences of the relaxation rates T−11 and T−11ρ are calculated for radial and bipolar nematic droplet structures. Special attention is given to the effect of the boundary layer nematic phase. Translationally induced modulation is in most cases an effective relaxation mechanism only in the low frequency range (〈MHz for micronsize droplets). The available experimental rotating-frame relaxation data are in excellent agreement with theoretical predictions.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 597-604 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The frequency and temperature dependences of the proton spin–lattice relaxation rate have been studied in nematic droplets embedded in a solid polymer matrix. The comparison of these data to those for bulk nematic and pure polymer samples shows that cross-relaxation between liquid crystal and polymer protons dominates the liquid crystal relaxation in the MHz frequency region, while at low frequencies the translationally induced molecular rotation becomes important. The cross-relaxation rate is found to be (approximate)103 s−1 giving an order of magnitude estimate 10−4–10−3 s for the time for which a liquid crystal molecule is bonded to the surface.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 86 (1987), S. 1055-1060 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The frequency dispersion and anisotropy of nuclear spin relaxation caused by order director fluctuations in the smectic A phase are calculated. Dispersion of (T−11)OF at low frequencies, which departs from the nematic-like behavior, is examined in detail and the influence of the wave vector dependent viscosity coefficients on relaxation is commented. The deviation from the nematic-like relaxation behavior drastically changes the angular dependence of (T−11ρ)OF.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Physics Letters A 79 (1980), S. 186-188 
    ISSN: 0375-9601
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Physics
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 100 (1994), S. 1693-1707 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Molecular dynamics of a main chain thermotropic liquid crystal polymer in the smectic A phase has been investigated using multipulse dynamic nuclear magnetic resonance (NMR) techniques. Transverse deuteron spin relaxation times T2ECP from quadrupole echo pulse trains (modified Carr–Purcell–Meiboom–Gill sequence) measured for deuterons in the aromatic rings of the mesogenic units are obtained as a function of pulse spacing τ sample orientation θN, and temperature. Just below the nematic–smectic A phase transition, the relaxation times exhibit a linear dispersion regime T2ECP ∼ τ−1 consistent with smectic director fluctuations. At lower temperatures, the dispersion step gradually disappears, indicating that faster molecular motions are the dominant transverse relaxation process. The observed anisotropy in T2ECP, measured at short pulse spacings, approximately follows the (sin4θN)−1 dependence expected for axial diffusion in a highly ordered medium. Analysis of the experiments is achieved employing a density operator treatment based on the stochastic Liouville equation. The intramolecular motion is identified with phenyl ring flips and is the fastest process studied, with correlation times varying from 10−10 to 10−7 s over the temperature range investigated.Intermolecular (individual molecule) dynamics are somewhat slower and have been interpreted as rotational diffusion in an orienting potential. The correlation times for intermolecular motion exhibit non-Arrhenius behavior approaching the glass transition, following a temperature dependence described by the Williams–Landel–Ferry equation over six orders of magnitude. This result indicates a strong coupling of the intermolecular motion to the glass transition process. The slowest motion affecting transverse deuteron spin relaxation is assigned to smectic director fluctuations or undulation waves. Analysis of the T2ECP dispersion yields information concerning the viscoelastic properties of the polymer. At T=418 K, a splay elastic constant of K1=2×10−11N has been estimated. Using the experimentally accessible value for the long wavelength cutoff of the elastic modes, the root mean square fluctuation 〈θ20〉1/2 of the director is calculated to be 4°.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 2154-2161 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The two-dimensional nuclear magnetic resonance (NMR) spectra and relaxation rates of polymer dispersed 4'-pentyl-4-cyanobiphenyl droplets deuterated in the β position of the hydrocarbon chain have been measured in the isotropic and nematic phases. A typical Pake power line shape pattern characteristic for a system of "bipolar'' droplets with a random distribution of their symmetry axes in the external magnetic field has been found in the ω2 domain whereas the homogeneous linewidth was observed in the ω1 domain. The existence of a weakly orientationally ordered surface layer above the nematic–isotropic transition has been demonstrated. Whereas the deuteron T1/T2(approximately-equal-to)4.3 in the isotropic phase, T1/T2(approximately-equal-to)188 in the nematic phase for confined droplets. This effect, which is absent in the bulk, shows that T2 is here mainly determined by translationally induced rotation in the nonuniformly oriented director field inside the cavity. T1, on the other hand, is determined by the slowing down of local molecular reorientations at the surface of the confined droplet as well as by local molecular fluctuations and rotations within the randomly oriented droplets.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 103 (1995), S. 8726-8733 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We report on the proton spin–lattice relaxation measurements in the isotropic and nematic phases of the liquid crystal 4′-pentyl-4-cyanobiphenyl (5CB), constrained by a low-concentration polymer network. Above the nematic–isotropic transition, a relatively small impact of the network in the MHz regime and a huge increase in the relaxation rate in the kHz regime are explained consistently by processes in the weakly orientationally ordered surface layer. A dynamic process with the correlation time ∼4×10−6 s is detected. The orientational order parameter in the surface layer is found to be almost temperature independent, and is estimated as S0∼0.1. The large internal surface-to-volume ratio of the liquid crystal in the dispersion, required for the explanation of experimental data, supports the simplified model which envisions the network elements as tiny fibers with nanometer radius. Comparison between NMR and optical data reveals mutual cross linking of the fibers. Measurements of the molecular self-diffusion constant indicate that fibers are distributed inhomogeneously on the submicrometer scale. © 1995 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 105 (1996), S. 4823-4832 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The frequency and temperature dependence of the longitudinal proton relaxation time T1 has been studied in liquid crystal droplets embedded in a solid polymer matrix in the nematic and isotropic phase over a broad Larmor frequency range (500 Hz≤νL≤84 MHz) employing the fast-field-cycling technique. The comparison of the droplet data, bulk 5CB data, and the pure polymer data show that T1 is dominated by the cross relaxation at the liquid crystal–polymer interface in the entire frequency range. In the low frequency range (νL≤1 MHz), an additional relaxation process determines T1 in both phases, namely reorientations mediated by translational replacements in the nematic phase and the exchange relaxation in the isotropic phase. The analysis of the cross relaxation rate k reveals that the simplified model of Vilfan is only applicable in the nematic phase and leads to an anchoring time τAS of the molecules at the surface which is ≈1.3×10−4 s. This model, however, cannot be applied in the isotropic phase, but must be extended by the spin diffusion time τP, which in this case determines the cross relaxation rate. The anchoring time τAS, which in the isotropic phase corresponds to the correlation time of the additional process, is much shorter than in the nematic phase, namely τAS≈10−6 s. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 98 (1993), S. 3540-3547 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Spin–lattice and spin–spin relaxation times of deuterium nuclei have been measured for a nematic liquid crystal confined in cylindrical channels of diameter 0.2 μm. In the isotropic phase the relaxation in the MHz regime is not affected by the confinement. The possibility of rotating the cylinders with respect to the magnetic field enables the first direct measurements of the anisotropy of deuteron relaxation of a monomeric liquid crystal in the nematic phase. The observed temperature dependence of the spin–spin relaxation rate in the isotropic phase roughly obeys the (T−T*)−1 law and allows the determination of the average time the molecules reside at the wall, which is 5×10−5 s for 5CB at the lecithin coated surfaces. In the nematic phase the spin–spin relaxation rate is affected by order director fluctuations and rotation induced by translational diffusion at orientations with a nonhomogeneous director distribution with respect to the magnetic field.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Journal of Molecular Structure 46 (1978), S. 475-480 
    ISSN: 0022-2860
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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