Molecular Self-diffusion Coefficients Research Articles

Crossover from gas-like to liquid-like molecular diffusion in a simple supercritical fluid.

According to textbooks, no physical observable can be discerned allowing to distinguish a liquid from a gas beyond the critical point. Yet, several proposals have been put forward challenging this view and various transition boundaries between a gas-like and a liquid-like behaviour, including the so-called Widom and Frenkel lines, and percolation line, have been suggested to delineate the supercritical state space. Here we report observation of a crossover from gas-like (Gaussian) to liquid-like (Lorentzian) self-dynamic structure factor by incoherent quasi-elastic neutron scattering measurements on supercritical fluid methane as a function of pressure, along the 200 K isotherm. The molecular self-diffusion coefficient was derived from the best Gaussian (at low pressures) or Lorentzian (at high pressures) fits to the neutron spectra. The Gaussian-to-Lorentzian crossover is progressive and takes place at about the Widom line intercept (59 bar). At considerably higher pressures, a liquid-like jump diffusion mechanism properly describes the supercritical fluid on both sides of the Frenkel line. The present observation of a gas-like to liquid-like crossover in the self dynamics of a simple supercritical fluid confirms emerging views on the unexpectedly complex physics of the supercritical state, and could have planet-wide implications and possible industrial applications in green chemistry.

Probing cellulose–solvent interactions with self-diffusion NMR: Onium hydroxide concentration and co-solvent effects

The molecular self-diffusion coefficients were accessed, for the first time, in solutions of microcrystalline cellulose, dissolved in 30 wt% and 55 wt% aqueous tetrabutylammonium hydroxide, TBAH (aq), and in mixtures of 40 wt% TBAH (aq) with an organic co-solvent, dimethylsulfoxide (DMSO), through pulsed field gradient stimulated echo NMR measurements. A two-state model was applied to estimate α (i.e., average number of ions that “bind” to each anhydroglucose unit) and Pb (i.e., fraction of “bound” molecules of DMSO, TBAH or H2O to cellulose) parameters. The α values suggest that TBA+ ions can bind to cellulose within 0.5 TBA+ to 2.3 TBA+/AGU. On the other hand, the Pb parameter increases when raising cellulose concentration for TBA+, DMSO and water in all solvent systems. Data suggests that TBAH interacts with the ionized OH groups from cellulose forming a sheath of bulky TBA+ counterions which consequently leads to steric hindrance between cellulose chains.

Prediction of self-diffusion coefficients of chemically diverse pure liquids by all-atom molecular dynamics simulations.

Molecular self-diffusion coefficients underlie various kinetic properties of the liquids involved in chemistry, physics, and pharmaceutics. In this study, 547 self-diffusion coefficients are calculated based on all-atom molecular dynamics (MD) simulations of 152 diverse pure liquids at various temperatures employing the OPLS4 force field. The calculated coefficients are compared with experimental data (424 extracted from the literature and 123 newly measured by pulsed-field gradient nuclear magnetic resonance). The calculations well agree with the experimental values. The determination coefficient and root mean square error between the observed and calculated logarithmic self-diffusion coefficients of the 547 entries are 0.931 and 0.213, respectively, demonstrating that the MD calculation can be an excellent industrial tool for predicting, for example, molecular transportation in liquids such as the diffusion of active ingredients in biological and pharmaceutical liquids. The self-diffusion coefficients collected in this study are compiled into a database for broad researches including artificial intelligence calculations.

Diffusion in dense supercritical methane from quasi-elastic neutron scattering measurements

Methane, the principal component of natural gas, is an important energy source and raw material for chemical reactions. It also plays a significant role in planetary physics, being one of the major constituents of giant planets. Here, we report measurements of the molecular self-diffusion coefficient of dense supercritical CH4 reaching the freezing pressure. We find that the high-pressure behaviour of the self-diffusion coefficient measured by quasi-elastic neutron scattering at 300 K departs from that expected for a dense fluid of hard spheres and suggests a density-dependent molecular diameter. Breakdown of the Stokes–Einstein–Sutherland relation is observed and the experimental results suggest the existence of another scaling between self-diffusion coefficient D and shear viscosity η, in such a way that Dη/ρ=constant at constant temperature, with ρ the density. These findings underpin the lack of a simple model for dense fluids including the pressure dependence of their transport properties.

Connecting molecular simulations and laboratory experiments for the study of time-resolved cation-exchange process in the interlayer of swelling clay minerals

In the context of element migration in clay-rich media, self-diffusion coefficients of interlayer cations in swelling clay minerals obtained from molecular simulations are rarely used by macroscopic models predicting cation-exchange processes. Based on experiments and simulations, this study aims at (i) making a connection between molecular and sample scale processes to predict the dynamics of cation-exchange reactions between the interlayer space of millimetre disks of vermiculite and aqueous reservoirs, and (ii) assessing the role played by both self-diffusion and selectivity coefficients on this process.Time-resolved cation exchange experiments were performed using Ca-saturated vermiculite disks immersed in aqueous reservoirs with different NaCl or SrCl2 salinities. The results were reproduced via a finite-volume model constrained by (i) cation self-diffusion coefficients calculated by molecular dynamics simulations and (ii) interlayer selectivity coefficients drawn from “batch” cation-exchange isotherms.Results showed that considering the averaged values for both the cation-exchange selectivity coefficients and self-diffusion coefficients of the slowest interlayer cation led to good agreement between the experiments and simulations, validating the modelling strategy for the connection between the molecular and laboratory time scales. A sensitivity test regarding the influence of the two input parameters on the overall results was then performed. This study underlined a constrained upscaling strategy to better assess the role played by different intrinsic parameters of the clay/water systems (molecular self-diffusion coefficients in the interlayer space vs. selectivity coefficient) on the diffusion of cations during cation-exchange reaction in clay-rich media.

Molecular dynamics simulations of nanodroplet evaporation of refrigerants

Abstract As the working fluid of energy transfer and conversion, refrigerants are essential in refrigeration and power systems. In order to improve the efficiency in power system, and reduce the design cost of evaporator, it is important to reveal the evaporation mechanism of refrigerants. In this study, the evaporation of R600 (butane), R134a (1,1,1,2-tetrafluoroethane), R32 (difluoromethane), and R1234yf (2,3,3,3-tetrafluoro-1-propene) was studied using molecular dynamics simulations. The internal fields such as density, radial mass fluxes of the molecular systems during the evaporation are compared. Besides, the prediction accuracy of the traditional diffusion-based model was evaluated. The results show that the prediction accuracy of traditional diffusion-based model is low due to the vapor thermal conductivity affected by the scale effect. A modified model based on vapor thermal conductivity with rarefied gas effect and interfacial influence is proposed to significantly improve the calculation accuracy for nanodroplet evaporation of different refrigerants. The evaporation rates of different refrigerants are affected by the molecular number density and molecular diffusion in the vapor phase near the interfacial region. The larger the molecular number density and the molecular self-diffusion coefficient are, the faster the droplet evaporation rate is.

Structural, rheological and dynamic aspects of hydrogen-bonding molecular liquids: Aqueous solutions of hydrotropic tert-butyl alcohol

HypothesisThe structural details, viscosity trends and dynamic phenomena in t-butanol/water solutions are closely related on the molecular scales across the entire composition range. Utilizing the experimental small- and wide-angle x-ray scattering (SWAXS) method, molecular dynamics (MD) simulations and the ‘complemented-system approach’ method developed in our group it is possible to comprehensively describe the structure-viscosity-dynamics relationship in such structurally versatile hydrogen-bonded molecular liquids, as well as in similar, self-assembling systems with pronounced molecular and supramolecular structures at the intra-, inter-, and supra-molecular scales. ExperimentsThe SWAXS and x–ray diffraction experiments and MD simulations were performed for aqueous t-butanol solutions at 25 °C. Literature viscosity and self-diffusion data were also used. FindingsThe interpretive power of the proposed scheme was demonstrated by the extensive and diverse results obtained for aqueous t–butanol solutions across the whole concentration range. Four composition ranges with qualitatively different structures and viscosity trends were revealed. The experimental and calculated zero-shear viscosities and molecular self-diffusion coefficients were successfully related to the corresponding structural details. The hydrogen bonds that were, along with hydrophobic effects, recognized as the most important driving force for the formation of t–butanol aggregates, show intriguing lifetime trends and thermodynamic properties of their formation.

Molecular Self-Diffusion Coefficients in Solutions of Dimethylsulfoxide in Monoethanolamine

The molecular self-diffusion coefficients of dimethylsulfoxide (DMSO) in monoethanolamine (MEA) are measured by means of proton NMR spin-echo spectroscopy at 304.6 K and DMSO concentrations varying from 0 to 30 mol %. The drop in the self-diffusion coefficient of MEA observed at low DMSO concentrations is attributed to the solvophobic effect DMSO molecules exhibit in solutions in MEA. The results obtained for the considered system are compared to similar data for the DMSO–ethylene glycol system. The differences between the two systems are explained by the higher lability of spatial hydrogen bond networks in liquid MEA, compared to ethylene glycol.

Multi-charge-state molecular dynamics and self-diffusion coefficient in the warm dense matter regime

We present a multi-ion molecular dynamics (MIMD) simulation and apply it to calculating the self-diffusion coefficients of ions with different charge-states in the warm dense matter (WDM) regime. First, the method is used for the self-consistent calculation of electron structures of different charge-state ions in the ion sphere, with the ion-sphere radii being determined by the plasma density and the ion charges. The ionic fraction is then obtained by solving the Saha equation, taking account of interactions among different charge-state ions in the system, and ion–ion pair potentials are computed using the modified Gordon–Kim method in the framework of temperature-dependent density functional theory on the basis of the electron structures. Finally, MIMD is used to calculate ionic self-diffusion coefficients from the velocity correlation function according to the Green–Kubo relation. A comparison with the results of the average-atom model shows that different statistical processes will influence the ionic diffusion coefficient in the WDM regime.

Cellulose–solvent interactions from self-diffusion NMR

Molecular self-diffusion coefficients were measured in solutions of microcrystalline cellulose (MCC) and dissolving pulp, in 40 wt% aqueous tetrabutylammonium hydroxide (TBAH), using pulsed field gradient stimulated echo NMR. From the cellulose diffusion coefficients, a weight averaged radius of hydration <Rh>w = 6.1 nm for MCC and <Rh>w = 15 nm for pulp were obtained. Water and TBA+ ions show a significantly different dependence on the cellulose concentration, revealing different molecular interactions with the polymer. Water-cellulose are essentially excluded volume. TBA+ ions, on the other hand, bind to cellulose with approximately 1.2 TBA+ ions per glucose unit.

Space-time scales in the Lagrange theory of thermal hydrodynamic fluctuations

The value and temperature dependence of the Maxwell relaxation time of viscous tensions and the Lagrangian particle radius, which are the main space-time scales in the Lagrange theory of thermal hydrodynamic fluctuations, are discussed. These parameters play the key role in the estimations of the relative value of the collective component of the molecular self-diffusion coefficient. Special attention is paid to the consistency of estimates obtained by different methods.

Suppressing magnetization exchange effects in stimulated-echo diffusion experiments

Exchange of nuclear magnetization between spin pools, either by chemical exchange or by cross-relaxation or both, has a significant influence on the signal attenuation in stimulated-echo-type pulsed field gradient experiments. Hence, in such cases the obtained molecular self-diffusion coefficients can carry a large systematic error. We propose a modified stimulated echo pulse sequence that contains T2-filters during the z-magnetization store period. We demonstrate, using a common theoretical description for chemical exchange and cross-relaxation, that these filters suppress the effects of exchange on the diffusional decay in that frequent case where one of the participating spin pools is immobile and exhibits a short T2. We demonstrate the performance of this experiment in an agarose/water gel. We posit that this new experiment has advantages over other approaches hitherto used, such as that consisting of measuring separately the magnetization exchange rate, if suitable by Goldman–Shen type experiments, and then correcting for exchange effects within the framework of a two-site exchange model. We also propose experiments based on selective decoupling and applicable in systems with no large T2 difference between the different spin pools.

Effects of incident cluster size, substrate temperature, and incident energy on bombardment of Ni clusters onto Cu (0 0 1) surface studied using molecular dynamics simulation

The bombardment process of a Ni cluster onto a Cu (001) surface is studied using molecular dynamics (MD) simulations based on the tight-binding second-moment approximation (TB-SMA) many-body potential. The effects of incident cluster size, substrate temperature, and incident energy are evaluated in terms of molecular trajectories, kinetic energy, stress, self-diffusion coefficient, and sputtering yield. The simulation results clearly show that the penetration depth and Cu surface damage increase with increasing incident cluster size for a given incident energy per atom. The self-diffusion coefficient and the penetration depth of a cluster significantly increase with increasing substrate temperature. An incident cluster can be scattered into molecules or atoms that become embedded in the surface after incidence. When the incident energy is increased, the number of volcano-like defects and the penetration depth increase. A high sputtering yield can be obtained by increasing the incident energy at high temperature. The sputtering yield significantly increases with cluster size when the incident energy is above 5eV/atom.

Diffusion Coefficients from (13)C PGSE NMR Measurements-Fluorine-Free Ionic Liquids with the DCTA(-) Anion.

Pulsed-field gradient spin-echo (PGSE) NMR is a widely used method for the determination of molecular and ionic self-diffusion coefficients. The analysis has thus far been limited largely to (1)H, (7)Li, (19)F, and (31)P nuclei. This limitation handicaps the analysis of materials without these nuclei or for which these nuclei are insufficient for complete characterization. This is demonstrated with a class of ionic liquids (or ILs) based on the nonfluorinated anion 4,5-dicarbonitrile-1,2,3-triazole (DCTA(-)). It is demonstrated here that (13)C-PGSE NMR can be used to both verify the diffusion coefficients obtained from other nuclei, as well as characterize materials that lack commonly scrutinized nuclei - all without the need for specialized NMR methods.

The role of tackifiers on the auto-adhesion behavior of EPDM rubber

The article describes the effect of hydrocarbon (HC) and coumarone-indene (CI) resin tackifiers on autohesion behavior of ethylene propylene diene polymethylene (EPDM) rubber. The viscoelastic behavior and nature of compatibility of EPDM/tackifier blends were studied by means of dynamic mechanical analysis. Furthermore, scanning electron microscopy and atomic force microscopy were used to understand the compatibility of the EPDM/tackifier blends. The HC tackifying resin modified the viscoelastic properties of the EPDM rubber in such a way that it behaved as a plasticizer at lower frequency by reducing the storage modulus and filler at higher frequency by increasing the storage modulus. On the contrary, the CI modified EPDM rubber did not show similar behavior; the modulus enhanced throughout the entire frequency range. The viscosity of the matrix was found to be highly governed by the compatibility as well as amount of tackifier present in the blend. In order to explain the tack behavior, several tack governing factors such as green strength, creep compliance, entanglement molecular weight, relaxation time, self-diffusion coefficient, and monomer friction coefficient (ζ0) were investigated. The tack strength increased with HC tackifier loading up to 24 parts per hundred grams of rubber (phr), beyond which a plateau region was observed. A maximum of 196% improvement was observed at 24 phr HC loaded sample as compared to gum EPDM rubber devoid of tackifier. Conversely, there was a marginal improvement of tack strength (36%) up to 8 phr loading for the system containing CI, beyond which it dropped.

Molecular motion and ion diffusion in choline chloride based deep eutectic solvents studied by 1H pulsed field gradient NMR spectroscopy

Deep Eutectic Solvents (DESs) are a novel class of solvents with potential industrial applications in separation processes, chemical reactions, metal recovery and metal finishing processes such as electrodeposition and electropolishing. Macroscopic physical properties such as viscosity, conductivity, eutectic composition and surface tension are already available for several DESs, but the microscopic transport properties for this class of compounds are not well understood and the literature lacks experimental data that could give a better insight into the understanding of such properties. This paper presents the first pulsed field gradient nuclear magnetic resonance (PFG-NMR) study of DESs. Several choline chloride based DESs were chosen as experimental samples, each of them with a different associated hydrogen bond donor. The molecular equilibrium self-diffusion coefficient of both the choline cation and hydrogen bond donor was probed using a standard stimulated echo PFG-NMR pulse sequence. It is shown that the increasing temperature leads to a weaker interaction between the choline cation and the correspondent hydrogen bond donor. The self-diffusion coefficients of the samples obey an Arrhenius law temperature-dependence, with values of self-diffusivity in the range of [10(-10)-10(-13) m(2) s(-1)]. In addition, the results also highlight that the molecular structure of the hydrogen bond donor can greatly affect the mobility of the whole system. While for ethaline, glyceline and reline the choline cation diffuses slower than the associated hydrogen bond donor, reflecting the trend of molecular size and molecular weight, the opposite behaviour is observed for maline, in which the hydrogen bond donor, i.e. malonic acid, diffuses slower than the choline cation, with self-diffusion coefficients values of the order of 10(-13) m(2) s(-1) at room temperature, which are remarkably low values for a liquid. This is believed to be due to the formation of extensive dimer chains between malonic acid molecules, which restricts the mobility of the whole system at low temperature (<30 °C), with malonic acid and choline chloride having almost identical diffusivity values. Diffusion and viscosity data were combined together to gain insights into the diffusion mechanism, which was found to be the same as for ionic liquids with discrete anions.

Interplay between bulk viscoelasticity and surface energy in autohesive tack of rubber-tackifier blends

The effects of change in surface energy and bulk viscoelastic properties on the autohesive tack strength of brominated isobutylene-co-p-methylstyrene (BIMS) rubber have been investigated by the addition of hydrocarbon resin (HCR) tackifier and maleated hydrocarbon resin (MA-g-HCR) tackifier. The addition of compatible HCR tackifier results in a reasonable increment in the tack strength of BIMS rubber by modifying only the bulk viscoelastic properties (compliance, entanglement molecular weight, relaxation time, self-diffusion, and monomer friction coefficient values) of BIMS rubber to perform better during the course of bonding and debonding steps of the peel test. Incorporation of MA-g-HCR tackifier (containing 5―20 wt % of grafted maleic anhydride) steadily increases the tack strength of BIMS rubber further by precisely modifying both the surface energy and bulk viscoelastic properties to perform much better in the bonding and debonding steps. However, beyond 20 wt % of grafted maleic anhydride in the HCR tackifier, the tack strength starts decreasing due to the incompatibility between the blend components, and hence, the bulk viscoelastic properties required for bond formation are severely retarded by the interrelated reinforcing effect and the phase separation effect of the brittle MA-g-HCR tackifier in the BIMS rubber. Hence, the polar groups in a tackifier will contribute to significant enhancement of autohesive tack strength only if the bulk viscoelastic property of the rubber-tackifier blend is favorable for bond formation and bond separation.

Efficacy of Novel Nanoclay in Autohesive Tack of Brominated Isobutylene-co-p-Methylstyrene (BIMS) Rubber

Autohesive tack is the ability of two unvulcanized rubber surfaces to resist separation after they are brought into contact for a short period under light pressure. In this work, the effect of unmodified montmorillonite (MMT) nanoclay on autohesive tack of brominated isobutylene-co-p-methylstyrene (BIMS) rubber was investigated by a 180° peel test. The nanocomposites were characterized using X-ray diffraction (XRD) and atomic force microscopy (AFM). The autohesive tack strength dramatically increased with nanoclay concentration up to 8 phr, beyond which it reached apparently a plateau at 16 phr of nanoclay concentration. The tack strength of 16 phr of nanoclay loaded sample was nearly 158% higher than the tack strength of neat BIMS rubber. Various tack governing factors such as green strength, creep compliance, entanglement molecular weight, relaxation time, self-diffusion coefficient, and monomer friction coefficient were analyzed. The addition of nanoclay reduced the extent of molecular diffusion at the tack junction by reducing the chain mobility; however, the diffusion was still sufficient to achieve bond formation. Furthermore, the less diffused chains of the nanocomposite samples showed greater bond breaking resistance due to an increase in cohesive strength, onset of transition zone relaxation time, and monomer friction coefficient value of the BIMS matrix owing to the nanoclay reinforcement. On the other hand, the more diffused chains of the unfilled sample exhibited facile chain separation due to the poor cohesive strength of the BIMS matrix.

Effect of Bulk Natural Convection on Chemical Processes Studied in a Tight Polymer Gel Reactor Composed of Polysaccharide Network and a Large Excess of Water

Abstract The effect of bulk natural convection on various chemical processes was investigated in a tight polysaccharide gel reactor composed of a few percent polysaccharide and excess water. It was elucidated that molecular self-diffusion coefficient (D cm2 s−1) in the gel is the same as in liquid water, but bulk natural convection is entirely prohibited making the molecular transport in these gels remarkably slower than in liquid water. Three-dimensional (3D) diffusion of Ru(bpy)32+ in a tight 0.125 wt % agarose gel took place only by molecular self-diffusion since bulk natural convection is prohibited, and the diffusion length agreed well with the theoretical 3-dimensional (3-D) self-diffusion length calculated from D. 2D diffusion of thionine in a polysaccharide gel also agreed well with the theoretical 2-D self-diffusion length showing also the absence of bulk natural convection. The chemical processes in the tight gel reactor in relevance to natural convection effects are discussed in terms of the time scale of the chemical process and the corresponding self-diffusion length of the reactants. For short time scale processes (ns to s) such as photochemical and electrochemical reactions, the process was not affected by bulk natural convection, but for a longer time scale (0.1 to 10 h) the effect of bulk natural convection was large.

Probing interactions by means of pulsed field gradient nuclear magnetic resonance spectroscopy

Molecular self-diffusion coefficients (D) of species in solution are related to size and shape and can be used for studying association phenomena. Pulsed field gradient nuclear magnetic resonance (PFG-NMR) spectroscopy has been revealed to be a powerful analytical tool for D measurement in different research fields. The present work briefly illustrates the use of PFG-NMR for assessing the existence of interactions in very different chemical systems: organic and organometallic compounds, colloidal materials and biological aggregates. The application of PFG-NMR is remarkable for understanding the role of anions in homogenous transition metal catalysis and for assessing the aggregation behaviour of biopolymers in material science.