Molecular diffusion, nuclear magnetic

A review is given of the application of Molecular Dynamics (MD) computer simulation to complex molecular systems. Three topics are treated in particular the computation of free energy from simulations, applied to the prediction of the binding constant of an inhibitor to the enzyme dihydrofolate reductase the use of MD simulations in structural refinements based on two-dimensional high-resolution nuclear magnetic resonance data, applied to the lac repressor headpiece the simulation of a hydrated lipid bilayer in atomic detail. The latter shows a rather diffuse structure of the hydrophilic head group layer with considerable local compensation of charge density. 

Nuclear magnetic resonance provides means to study molecular dynamics in every state of matter. When going from solid state over liquids to gases, besides mole- cular reorientations, translational diffusion occurs as well. CD4 molecule inserted into a zeolite supercage provides a new specific model system for studies of rotational and translational dynamics by deuteron NMR. 

Some of the methods for measuring molecular diffusion coefficients, together with a few recent references, are (a) diaphragm cell [60,61] (b) boundary layer interferometry [59] (c) shearing plate interferometry [58] (d) chromatographic peak broadening [60] (e) nuclear magnetic resonance and electron spin resonance [62, 63] (f) electrolyte conductance [64] (g) isotopic tracers [65] and (h) laminar jets [66]. 

Let us mention several papers by Ya.B. on various problems of molecular physics and quantum mechanics which have not been included in this volume. Among the problems considered are the peculiar distribution of molecules according to their oscillatory modes when the overall number of oscillatory quanta does not correspond to the temperature of translation [9], the influence of the nuclear magnetic moment on the diffusion coefficient [10] and on absorption of light by prohibited spectral lines [11],... 

Abstract We use Nuclear Magnetic Resonance relaxometry (i.e. the frequency variation of the NMR relaxation rates) of quadrupolar nucleus ( Na) and H Pulsed Gradient Spin Echo NMR to determine the mobility of the counterions and the water molecules within aqueous dispersions of clays. The local ordering of isotropic dilute clay dispersions is investigated by NMR relaxometry. In contrast, the NMR spectra of the quadrupolar nucleus and the anisotropy of the water self-diffusion tensor clearly exhibit the occurrence of nematic ordering in dense aqueous dispersions. Multi-scale numerical models exploiting molecular orbital quantum calculations, Grand Canonical Monte Carlo simulations, Molecular and Brownian Dynamics are used to interpret the measured water mobility and the ionic quadrupolar relaxation measurements. 

The formation of complex ions is an important problem for the study of the structure and properties of molten salts. Several physicochemical measurements give evidence of the presence of complex ions in melts. The most direct methods are the spectroscopic methods which obtain absorption, vibration and nuclear magnetic resonance spectra. Also, the formation of complex ions can be demonstrated, without establishing the quantitative formula of the complexes, by the variation of various physicochemical properties with the composition. These properties are electrical conductivity, viscosity, molecular refraction, diffusion and thermodynamic properties like molar volume, compressibility, heat of mixing, thermodynamic activity, surface tension. 

The process of molecular diffusion may be viewed conceptionally as a sequence of jumps with statistically varying jump lengths and residence times. Information about the mean jump length /(P and the mean residence time t, which might be of particular interest for a deeper understanding of the elementary steps of catalysis, may be provided by spectroscopic methods, in particular by quasielastic neutron scattering (see next Section) and nuclear magnetic resonance (NMR). 

Figure 16.25. Motion-sensitized proton images of water flowing in a tube. The top image gives the velocity (vertical direction) at each point in the tube cross section, the middle image gives the molecular diffusion coefficient, and the bottom shows the expected parabolic velocity profile across the tube diameter. (Reprinted with permission from Callaghan PT. Principles of Nuclear Magnetic Resonance Microscopy. Oxford University Press, New York, 1991. Copyright 1991 Oxford University Press.)...

Spectroscopic methods, such as FT-infrared (FTIR) and Raman spectroscopy detect changes in molecular vibrational characteristics in noncrystalline solid and supercooled liquid states. Various nuclear magnetic resonance (NMR) techniques and electron spin resonance (ESR) spectroscopy, however, are more commonly used, detecting transition-related changes in molecular rotation and diffusion (Champion et al. 2000). These methods have been used for studies of the amorphous state of a number of sugars in dehydrated and freeze-concentrated systems (Roudaut et al. 2004). 

Jost S, Bar NK, Fritzsche S, Haberlandt R, and Karger J. Diffusion of a mixture of methane and xenon in silicalite A molecular dynamics study and pulsed field gradient nuclear magnetic resonance experiments. J Phys Chem B 1998 102 6375-6381. 

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