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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 10809-10817 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Field cycling nuclear magnetic resonance relaxometry was used to study the slow molecular dynamics in the nematics and isotropic phases and polyphasic region of the phase diagram in the thernary mixture: potassium laurate/1-decanol/water. The experiment has been performed over a broad range of Larmor frequencies (2×103−6.6×106 Hz). The first experimental evidence of director fluctuations in a micellar lyotropic nematic liquid crystal, studied by 1H spin-lattice relaxation rate, is reported. The results evidence that in the nematic mesophases, director fluctuations are responsible for the spin-lattice relaxation dispersion in the low Larmor frequency range ((approximately-less-than)105 Hz). By increasing the intermicellar water content, a crossover was found between a quasi-isotropic three-dimensional (3D) director fluctuation behavior and a two-dimensional (2D) pseudo-lamellar undulation fluctuation. In spite of the fact that no menatic phases of this micellar complex fluid are isotropic with respect to light scattering, they present spin-lattice relaxation profiles as driven by local director fluctuations. The polyphasic region, at lower temperatures, shows a quasinematic 3D director fluctuation behavior; meanwhile, the isotropic phase, at higher temperatures, presents 2D pseudo-lamellar undulation fluctuation modes. We conclude that the micelles, in the isotropic phase, preserve the pseudo-lamellar structure, already found in the nematic phases but forming nematic domains with the directors randomly oriented. In order to explain the higher frequency range ((approximately-greater-than)105 Hz), two relaxation mechanisms are assigned: (i) molecular reorientation by translational diffusion on the micellar surface and (ii) molecular exchange between the micelle and the bulk. © 2000 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Chemical Physics Letters 183 (1991), S. 183-186 
    ISSN: 0009-2614
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology , Physics
    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 109 (1998), S. 1120-1124 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Larmor frequency dependent NMR studies of dipolar order relaxation in liquid crystals have seldom been tried in the past. Using conventional static magnetic field techniques, the experiment cannot be extended to the low Larmor frequency (νL) regime due to limitations in the signal-to-noise ratio of the dipolar echo. In this work, we present an experimental study of the dipolar relaxation time in the frequency range 103–7×107 Hz in nematic thermotropic liquid crystals. To extend the study to such low frequencies, we used the Jeener–Broekaert pulse sequence combined with fast field-cycling NMR technique. For frequencies higher than 105 Hz, the dipolar relaxation time T1D(νL) follows the νL1/2-law that is characteristic of order fluctuations of the director (OFD) in nematics. In contrast, the Zeeman relaxation is driven by faster and less correlated motions, specially in the MHz frequency range. The relaxation of dipolar energy was measured to be remarkably faster than the one predicted by the usual semiclassical model of isolated spin pairs. Conceivably, the failure of the usual two-spin model should be sought in the absence of multispin interactions and multispin correlations. We propose that the OFD are the dominant relaxation mechanism for the dipolar order, even in the MHz regime. This result turns T1D(νL) experiment in a useful NMR technique for the study of slow molecular dynamics in mesophases. © 1998 American Institute of Physics.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 108 (1998), S. 1881-1885 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Nutation nuclear quadrupole resonance spectroscopy enables one to determine the asymmetry parameter on powder samples. The method relies on two-dimensional methodology: The first period is the duration of the radio frequency exciting pulse and the second dimension is the free-evolution period of the quadrupolar nucleus. Varying lengths of the radio frequency pulse induce an amplitude modulation of the free-induction decay signals which is characteristic of the anisotropic nutation frequency distribution. Fourier analysis along the first dimension provides a powder nutation line shape that allows determination of the electric field gradient tensor's asymmetry parameter. We describe the first application of two-dimensional phase-modulated spectroscopy to a quadrupolar nucleus at zero field. It is shown that a phase-modulated variant of the nutation spectroscopy is feasible in the pure quadrupole regime and it provides a gain in the signal-to-noise ratio compared to the amplitude-modulated method. © 1998 American Institute of Physics.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 110 (1999), S. 8155-8160 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Larmor frequency dependent measurements of Zeeman (T1Z) and dipolar order (T1D) relaxation times provide experimental information on the molecular dynamics in liquid crystals. However, at present, a comprehensive theoretical expression relating T1D with the spectral densities of the molecular motions is not available for liquid crystals. In fact, recent relaxation studies in nematic thermotropic liquid crystals have shown that the traditional model of isolated phenyl proton pairs predicts a relaxation of the dipolar order noticeably slower than the observed one. In this work we show that the failure cannot be assigned exclusively to the assumption of isolated spin-pairs. With this aim, we study the dipolar order relaxation in the nematic PAAd6 (methyl deuterated para-azoxyanizole). After calculating a generalized expression for T1D valid for an arbitrary number of spins, we found that the contributions from multispin interactions and correlations are negligible. This means that, from the point of view of the traditional weak collision theory of relaxation, PAAd6 provides an example of an ensemble of isolated spin-pairs. Nevertheless, after measuring T1D over a broad frequency range (103–3×107 Hz), we found a faster relaxation than predicted by the two-spin model, even in this compound. We conclude, therefore, that the failure of the model should be ascribed to basic assumptions of the traditional semiclassical model of spin-lattice relaxation in liquid crystals © 1999 American Institute of Physics.
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 106 (1997), S. 2096-2100 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A novel one-dimensional nuclear quadrupole resonance experiment to measure the asymmetry parameter of the electric field gradient tensor in polycrystalline specimens using nutation spectroscopy is reported. The complete data set, necessary for the reconstruction of the powder nutation lineshape, is recorded in a single scan provided by a train of short and intense on-resonance radiofrequency pulses. A modified scheme is presented to deal with multiple well-resolved resonances to provide a frequency selective nutation method. The technique is successfully demonstrated for the two 35Cl resonances in cyanuric chloride. A reduction of 1 or 2 orders of magnitude in the data acquisition time, relative to the usual two-dimensional method, is achieved. © 1997 American Institute of Physics.
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  • 7
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Journal of Magnetic Resonance (1969) 91 (1991), S. 630-636 
    ISSN: 0022-2364
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Physics
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 1572-8854
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The molecular structure of 2,4,5-trichlorobenzenesulfonyl chloride has been determined by X-ray diffraction methods. The compound is orthorhombic,Aba2, witha=16.253(12),b=17.016(9),c=7.146(5) Å,V=1976(5) Å3,Z=8,D=1.88 kg·mm−3, (MoKα)=0.7107 Å,μ=136.8 cm−1,F(000)=1104. Data were obtained at room temperature; the finalR is 0.029 for 854 independent reflections. The substituted benzene ring is planar within experimental accuracy, the dihedral angle with the C(1)-S(1)-Cl(1) plane being 66.0(5)°. The compound has normal bond lengths and angles; some short intramolecular distances account for the maintenance of the rigid benzene frame. No significatively short intermolecular distances have been found. Confirmation of the oscillatory character of the semiexternal molecular motions operating above 180 K is accounted for.
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  • 9
    Publication Date: 2002-02-08
    Print ISSN: 1063-651X
    Electronic ISSN: 1095-3787
    Topics: Physics
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  • 10
    Publication Date: 1996-05-20
    Print ISSN: 0031-9007
    Electronic ISSN: 1079-7114
    Topics: Physics
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