Search results for "Self-diffusion"
showing 10 items of 34 documents
Fick Diffusion Coefficients in Ternary Liquid Systems from Equilibrium Molecular Dynamics Simulations
2012
An approach for computing Fick diffusivities directly from equilibrium molecular dynamics (MD) simulations is presented and demonstrated for a ternary chloroform–acetone–methanol liquid mixture. In our approach, Fick diffusivities are calculated from the Maxwell–Stefan (MS) diffusivities and the so-called matrix of thermodynamic factors. MS diffusivities describe the friction between different molecular species and can be directly computed from MD simulations. The thermodynamic factor describes the deviation from ideal mixing behavior and is difficult to extract from both experiments and simulations. Here, we show that the thermodynamic factor in ternary systems can be obtained from density…
Self-diffusion coefficients in plastic crystals by multiple-pulse NMR in large static field gradients.
1996
Measurements of self-diffusion coefficients in solids with the gradient spin echo technique have until now been limited due to short spin-spin relaxation times. Here we make use of multiple-pulse sequences, which average out the nuclear dipole interaction, to expand the measurable range for macroscopic self-diffusion coefficients by 2 orders of magnitude. By combining multiple-pulse NMR, in our case using the MREV-8 sequence, with a high static gradient we measured the self-diffusion coefficient in a molecular crystal of camphene down to a value of $D\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}3\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}16}{\mathrm{m}}^{2}{\mathrm{s}}^{\en…
Single-File Diffusion of Colloids in One-Dimensional Channels
2004
We study the diffusive behavior of colloidal particles which are confined to one-dimensional channels generated by scanning optical tweezers. At long times t, the mean-square displacement is found to scale as t(1/2), which is expected for systems where single-file diffusion occurs. In addition, we experimentally obtain the long-time, self-diffusive behavior from the short-time collective density fluctuations of the system as suggested by a recent analytical approach [Phys. Rev. Lett. 90, 180602 (2003)]. published
Translational and rotational diffusion in supercooled orthoterphenyl close to the glass transition
1992
Self diffusion coefficients in supercooled orthoterphenyl (OTP) have been determined down toD t =3·10−14 m2s−1 using a1H-NMR technique applying static field gradients up to 53T m−1 In a range of more than two decades theD t values agree with those of photochromic tracer molecules of the same size determined by forced Rayleigh scattering down to the glass transition temperatureT g . A change of mechanism is found for translational diffusion atT c ≈1.2T g whereD t is proportional to the inverse shear viscosityη −1 atT>T c butD t ∼η ξ with ξ=0.75 atT<T c . Rotational correlation times determined by2H-NMR stimulated echo techniques in deuterated OTP remain proportinal toη −1 down toT g . Our re…
Monte Carlo simulations of polymer dynamics: Recent advances
1997
A brief review is given of applications of Monte Carlo simulations to study the dynamical properties of coarse-grained models of polymer melts, emphasizing the crossover from the Rouse model toward reptation, and the glass transition. The extent to which Monte Carlo algorithms can mimic the actual chain dynamics is critically examined, and the need for the use of coarse-grained rather than fully atomistic models for such simulations is explained. It is shown that various lattice and continuum models yield qualitatively similar results, and the behavior agrees with the findings of corresponding molecular dynamics simulations and experiments, where available. It is argued that these simulatio…
Dynamic anomalies at the glass transition of organic van der Waals liquids
1993
Abstract The paper discusses the question of whether there is a characteristic temperature T c above the calorimetric glass transition temperature T g . Mode-coupling theory (MCT) predicts a crossover from liquid- to solid-like dynamics at T c . Neutron scattering and gradient NMR experiments have been carried out to test MCT using the molecular van der Waals liquid ortho -terphenyl as a model system. A significant anomaly of the Debye—Waller factor and a “decoupling” of self-diffusion from viscosity support the MCT predictions. A critical discussion of the relevance of such tests and of the limitations of neutron scattering is presented.
Heterogeneity at the Glass Transition: Translational and Rotational Self-Diffusion
1997
Self-diffusion coefficients, D, have been measured in the glass forming liquids salol, glycerol, phenolphthaleine dimethyl ether (PDE), cresolphthaleine dimethyl ether (CDE), and ααβ-trinaphthylbenzene (TNB) in the supercooled regime. The NMR static magnetic field gradient technique was applied where D >10-14 m2 s-1 can be attained. The results are similar to previous diffusion experiments where an enhancement of translational diffusion was found in comparison with rotational diffusion and shear viscosity. Various models of spatial heterogeneity are related to a phenomenological environmental fluctuation model in view of recent diffusion and relaxation data close to the glass transition.
Surface Self-Diffusion and Mean Displacement of Hydrogen on Graphite and a PEM Fuel Cell Catalyst Support
2009
International audience; Quasielastic neutron scattering (QENS) measurements together with equilibrium molecular dynamic (EMD) simulations have been performed to investigate the surface interaction between hydrogen molecules and a carbon material commonly used in polymer electrolyte membrane fuel cells (PEMFC), called XC-72. Half a monolayer of molecular hydrogen was adsorbed on to the carbon material at 2 K. QENS spectra were recorded at the time-of-flight spectrometer IN5 at 40, 45, 50, 60, 70, 80, and 90 K. Simultaneously the pressure was measured as a function of time to monitor the equilibrium surface coverage at each temperature. By using the Chudley and Elliott model for jump diffusio…
Collective and self diffusion of PS microgels in solution as observed by thermal diffusion forced Rayleigh scattering
2007
Thermal diffusion in solutions of polystyrene micro-network spheres (microgels) in toluene has been studied by the holographic scattering technique of thermal diffusion forced Rayleigh scattering (TDFRS) and by photon correlation spectroscopy (PCS). Size distributions of microgels of different crosslink ratios are obtained from TDFRS measurements on dilute solutions at very low q-values around 4000cm−1. At low concentrations a single diffusive mode is observed and the diffusion coefficient increases with concentration. It is attributed to the collective diffusion of the microgels and the solvent. At high concentrations an additional slow mode appears whose diffusion coefficient decreases wi…
Si self-diffusion in cubic B20-structured FeSi
2008
Self-diffusion of implanted 31Si in the e-phase FeSi (cubic B20-structure) has been determined in the temperature range 660–810 °C using the modified radiotracer technique. With an activation enthalpy of 2.30 eV and a pre-exponential factor of 15×10−8 m2 s−1 the silicon diffusivity was found to be slightly slower than Ge impurity diffusion in FeSi. This difference is proposed to originate from attractive elastic interactions prevailing between the slightly oversized Ge atoms and the Si sublattice vacancies. The results confirm the argument that 71Ge radioisotopes may be used to substitute the short-lived 31Si radiotracers when estimating self-diffusion in silicides.