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  • 1
    ISSN: 1520-510X
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Inorganic chemistry 26 (1987), S. 3221-3224 
    ISSN: 1520-510X
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    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 102 (1995), S. 947-955 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Dipolar interactions among nuclear magnetic moments embedded in rigid solids are examined. Substitutional disorder in lattices is shown to modify the statistical properties of the distributions of the absolute values of dipolar coupling constants. Numerical studies reveal that a crossover in the average of the coupling constants in dilute spin networks occurs as a function of the random fractional occupancy in the lattice. The origin of this crossover is related to an interplay between the statistical weights of the coupling constants and their values which are distributed over many orders of magnitude. Two different regimes of behavior are observed for the average of the coupling constants as a function of dilution; one regime is dominated by the most probable value of the distribution of coupling constants, while in the other regime, the arithmetic mean prevails. For a macroscopic sample of 1022 sites, the crossover between regimes is predicted to occur when 1011 sites are occupied. Averaging over the substitutional disorder is also investigated. It is suggested that the character of the fluctuations in the disorder average could possibly serve to establish when a measurement on a large system is equivalent to an ensemble average over the subsystems of a sample. An analogous dynamic crossover, originating from similar behavior in the statistical properties of distributions of products of dipolar coupling constants, is pointed out for multiple quantum nuclear magnetic resonance (NMR) spectroscopy of solids. © 1995 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 95 (1991), S. 7071-7078 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , 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 104 (1996), S. 2000-2009 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Some analytical results, concerning the disorder average of magnetic dipolar interactions in dilute spin networks and valid in the thermodynamic limit, are derived within a mean field approximation. In particular, it is shown that the quenched substitutional disorder average of the free induction decay of the nuclear magnetization in such a homonuclear spin system yields, 〈G(t)〉c ∼ exp[−ρ(γ2(h-dash-bar)t)D/3], where ρ is the concentration of magnetic nuclei embedded in a D-dimensional space and γ the nuclear magnetogyric ratio. Furthermore, the relative fluctuations about the disorder average, {[〈G2(t)〉c−〈G(t)〉2c]1/2/〈G(t)〉 ic}, scale as [ρ1/2(γ2(h-dash-bar)t)D/6/N1/2], when ρ(γ2(h-dash-bar)t)D/3(very-much-less-than)1, and as N−1/2 exp[ρ(γ2(h-dash-bar)t)D/3] [1+ρ−3(γ2(h-dash-bar)t)−D]1/2 when ρ(γ2(h-dash-bar)t)D/3(very-much-greater-than)1; N is the number of spins in the lattice. The distinction between the role of the arithmetic mean and the most probable value of the distribution of dipolar coupling constants in the configurational averages of the free induction decay and its relative fluctuations is pointed out. Implications for nuclear magnetic resonance (NMR) experiments in magnetically diluted solids are also examined. © 1996 American Institute of Physics.
    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 103 (1995), S. 2670-2687 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The domain growth processes occurring during the gravity-dominated regime of the phase separation of a cyclohexane/aniline critical mixture, following a temperature quench in the unstable region below the temperature-composition coexistence curve, were investigated with high-resolution 1H NMR. Diffusive exchange of cyclohexane molecules between a small volume fraction of immiscible droplets and the surrounding fluid with a different cyclohexane concentration leads to a domain-size dependent 1H NMR cyclohexane chemical shift in the continuous phase. In this case, the equations of motion for the transverse magnetization density reduce to a first-order exchange between two immiscible phases with rate coefficients depending on the droplet size and the transport process across the liquid–liquid interface. Application of this model to the data yields a power law for the growing droplets, R(t)=Atφ, where R is a typical domain size, with the growth exponent φ=0.30±0.01 and the amplitude A(approximately-equal-to)0.9×10−6 ms−φ. These values are in close agreement with previous visualization studies on the same binary mixture [F. Cau and S. Lacelle, Phys. Rev. E 47, 1429 (1993)]. The results also confirm the presence of a new domain growth regime involving Brownian coagulation and sedimentation in the very late stage of the phase separation processes of binary liquid mixtures. A strong linear composition dependence of the 1H NMR cyclohexane chemical shift in one-phase cyclohexane/aniline mixtures was interpreted on the basis of solvent shift effects induced by intermolecular interactions and susceptibility effects. In each phase of the two-phase equilibrium mixture, inhomogeneous line broadening, arising from the magnetic susceptibility discontinuity at the interface between phases, is also investigated. © 1995 American Institute of Physics.
    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 107 (1997), S. 7067-7084 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Multiple quantum (MQ) nuclear magnetic resonance (NMR) spin dynamics are investigated analytically in infinite one-dimensional (1D) chains of spins 1/2. The representation of spin 1/2 operators with fermion field operators allows to calculate exactly the spin density operator, and hence NMR observables, under a variety of different conditions for 1D spin systems. The exact expressions are valid for all times and for a macroscopic number of coupled spins. The calculations for a 1D spin system initially at thermal equilibrium, and evolving under a 2-quantum/2-spin average dipolar Hamiltonian, in the presence of nearest-neighbor dipolar interactions yield MQ NMR spectra with 0- and 2-quantum coherences only. For a nonequilibrium initial condition with transverse magnetization, the analogous spin dynamics calculations produce MQ NMR spectra with all possible coherences of odd orders. Calculations at the level of perturbation theory, which include next-nearest-neighbor dipolar interactions, generate MQ spectra with higher even order coherences for equilibrium initial condition and evolution under a 2-quantum/2-spin propagator. Consideration of multiple spin correlations, 0-quantum coherences, and rf pulse imperfections are also presented. The relevance and implications of these theoretical results for comparison with the recent MQ NMR experiments of Yesinowski et al. on materials with quasi-one-dimensional distributions of spins, and for MQ NMR of solids in general are discussed. © 1997 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 99 (1993), S. 8407-8413 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The conventional method of data analysis and interpretation of time-resolved multiple quantum (MQ) nuclear magnetic resonance (NMR) spectra of solids is closely examined. Intensity profiles of experimental 1H MQ NMR spectra of polycrystalline adamantane and hexamethylbenzene serve to test the Gaussian statistical model approach. Consequences of this model are explored with a least-squares fitting procedure, transformation of data to yield linear plots, and a scaling analysis. Non-Gaussian behavior of the MQ NMR spectral intensity profiles, as a function of order of coherences, is demonstrated with all these methods of analysis. A heuristic argument, based on the multiplicative properties of dipolar coupling constants in the equation of motion of the density operator, leads to the prediction of exponentially decaying MQ NMR spectral intensity profiles. Scaling analysis and semilog plots of experimental time-resolved MQ NMR spectra of adamantane and hexamethylbenzene support this deduction. Dynamical scale invariance in the growth process of multiple spin coherences is revealed with this new approach. The validity of spin counting in solids with MQ NMR is discussed in light of the present results.
    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. 3642-3649 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Some statistical properties of the distributions of dipolar coupling constants and their products are discussed in the context of nuclear magnetic resonance (NMR) of solids. Transformations of the distributions (absolute values and their logarithms) reveal new statistical properties. The "relative fluctuations'' of the absolute value distributions, i.e., (second absolute central moment)1/2/(first absolute moment) are shown to scale as N+1/2, where N is the number of spins. The ratio (first absolute moment)/(most probable value) is shown to diverge as N+3/2. Products of the absolute values of dipolar coupling constants follow lognormal distributions in large spin networks. The relative fluctuations of these products also scale with N+1/2. Numerical studies of spin systems, with 10≤N≤105, in one-, two-, and three-dimensional crystalline lattices support several of these results. Some implications for multiple quantum NMR spectroscopy are presented.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 26 (1987), S. 849-861 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A variety of nmr transient techniques demonstrate the absence of domain structures in powders of α- and β-cyclodextrins, dextran B512F, and their “deuterated” analogs where deuterium replaces exchangeable protons. Cyclodextrins and dextran are inferred to be homogeneously ordered and disordered one-phase systems, respectively. We show how erroneous results concerning the presence and sizes of rigid and mobile domains can be reached from the interpretations of two-component free induction decays and spin-lattice relaxation behavior of polysaccharides. In our approach, we have measured 1H free induction decays and lineshapes, and 1H spin-lattice and dipolar relaxation times, in addition to using Goldman-Shen experiments and 13C cross-polarization magic-angel sample spinning. Self-consistent nmr results are suggested as essential means to corroborate conclusions concerning domain structures in biopolymers.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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