Monte Carlo and Molecular Dynamics

Glass-forming liquids exhibit a rich phenomenology upon onfinement. This is often related to the effects arising from wall–fluid interactions. Here we focus on the interesting limit where the separation of the confining walls becomes of the order of a few particle diameters. For a moderately polydisperse, densely packed hard-sphere fluid confined between two smooth hard walls, we show via event-driven molecular dynamics simulations the emergence of a multiple reentrant glass transition scenario upon a variation of the wall separation. Using thermodynamic relations, this reentrant phenomenon is shown to persist also under constant chemical potential. This allows straightforward experimental investigation and opens the way to a variety of applications in micro- and nanotechnology, where channel dimensions are comparable to the size of the contained particles. The results are in line with theoretical predictions obtained by a combination of density functional theory and the mode-coupling theory of the glass transition.

Atomistic, molecular dynamics simulations of water diffusion in a hydrated, amorphous polyamide have been carried out to study the effects of polymer dynamics, cross-linking, and hydrogen bonding interactions on the molecular mechanisms of diffusion. This polymer was selected as a model for the discriminating layer of FT-30 reverse osmosis membranes, used commercially for water desalination. Analysis of the configurations generated during the simulations shows that, at the relatively high water content studied, a continuous water phase is formed which permeates the polymer and consists of more than 90% of all waters of hydration. Water diffusion takes place by distinct " jump-like " movements between weakly localized sites in this continuous phase. The jump length is on average 3Å , independent of the system studied, and is most likely defined by the local, cooperative rearrangement of water molecules. However, the jump frequency, or equivalently , the rate of water diffusion varies from system to system, and depends on polymer dynamics and cross-linking density, and more significantly, on water–water hydrogen bonding interactions.

Constrained molecular dynamics simulations have been performed to investigate the structure and thermodynamics of Na(+)-Cl(-) ion-pair association in water-methanol mixtures under supercritical and ambient conditions in dilute solutions. From the computed potentials of mean force (PMFs) we find that contact ion pairs (CIPs) are more stable than all other associated states of the ion pairs in both ambient and supercritical conditions. Stabilities of CIPs increase with increase in the mole fraction of methanol. In supercritical conditions, major changes in PMFs occur as we go from x(methanol) = 0.00 to x(methanol) = 0.50. The stable solvent shared ion pair (SShIP) which occurs in x(methanol) = 0.00 and 0.25, vanishes when x(methanol) is 0.50 or greater. The stabilities of these ion pairs increase with increasing temperature. Local structures around the ions are studied using the radial distribution functions, density profiles, angular distribution functions, running coordination numbers and excess coordination numbers. Preferential solvation analysis shows that both Na(+) and Cl(-) ions are preferentially solvated by water. From the calculation of enthalpies and entropies, we find that Na(+)-Cl(-) ion-pair association in water-methanol binary mixtures is endothermic and driven by entropy both in ambient as well as under supercritical conditions.

The effect of new terms in the improved algorithm, the modified direct simulation Monte-Carlo (MDSMC) method, is investigated by simulating a rarefied binary gas mixture flow inside a rotating cylinder. Dalton law for the partial pressures contributed by each species of the binary gas mixture is incorporated into our simulation using the MDSMC method and the direct simulation Monte-Carlo (DSMC) method. Moreover, the effect of the exponent of the cosine of deflection angle (a) in the inter molecular collision models, the variable soft sphere (VSS) and the variable hard sphere (VHS), is investigated in our simulation. The improvement of the results of simulation is pronounced using the MDSMC method when compared with the results of the DSMC method. The results of simulation using the VSS model show some improvements on the result of simulation for the mixture temperature at radial distances close to the cylinder wall where the temperature reaches the maximum value when compared with the results using the VHS model.

Exposure of polymethylmethacrylate (PMMA) during electron beam lithography (EBL) produces small polymer fragments that dissolve rapidly during the development process. The resist dissolution behavior varies greatly depending on the nature of the developer (solvent) and therefore influences the selection of the EBL parameters, such as dose (sensitivity). A molecular scale examination of the development process is necessary to elucidate the resist–developer interaction mechanisms. In this work, the authors investigate the interaction of short PMMA chains (containing up to 10 MMA units) with common developer components methyl isobutyl ketone (MIBK) and isopropyl alcohol (IPA). For this purpose, the authors conduct molecular dynamics simulations using the Accelrys Materials Studio package. The simulation results were used to characterize the mixtures in the spirit of the Flory–Huggins theory of polymers and also to extract the diffusivities. The authors found that the behavior of PMMA fragments differed considerably in MIBK as compared with IPA. PMMA fragments containing more than three monomers exhibit stronger attractive interaction with MIBK. For all fragment sizes simulated, the diffusivity of PMMA fragments is 60–160% higher in MIBK as well. Similarly, the authors observed differences in the gyration radii. The authors conclude that the kinetic factor seems to be more significant as compared to affinity factor when accounting for differences in exposure sensitivities due to developer selection.

Constrained molecular dynamics simulations have been performed to investigate the structure and thermodynamics of Na+ - Cl- ion-pair association in water-methanol mixtures in supercritical and ambient conditions in dilute solutions. From the computed potentials of mean force (PMFs) we find that contact ion pairs (CIPs) are more stable than all other associated states of the ion pairs in both ambient and supercritical conditions. Stabilities of CIPs increase with increase with the mole fraction of methanol. In supercritical conditions, major changes in PMFs occur as we go from xmethanol = 0.00 to xmethanol = 0.50. The stable solvent shared ion pair (SShIP) which occurs in xmethanol = 0.00 and 0.25, vanishes when xmethanol is 0.50 or greater. The stabilities of these ion pairs increase with increasing temperature. Local structures around the ions are studied using the radial distribution functions, density profiles, angular distribution functions, running coordination numbers and excess coordination numbers. Preferential solvation analysis shows that both Na+ and Cl- ions are preferentially solvated by water. From the calculation of enthalpies and entropies, we find that Na+ - Cl- ion-pair association in water-methanol binary mixtures is endothermic and driven by entropy both in ambient as well as in supercritical conditions.

Porous structures of silica aerogels are generated using classical molecular dynamics, with the Tersoff potential, which has been re-parametrized for modeling silicon dioxides. This work demonstrates that this potential is superior to the widely used BKS potential in terms of characterizing the thermal conductivities of amorphous silica, by comparing the vibrational density of states with previous experimental studies. Aerogel samples of increasing densities are obtained through an expanding, heating and quenching process. Reverse non-equilibrium molecular dynamics is applied at each density to determine the thermal conductivity. A power-law fit of the results is found to accurately reflect the power-law variation found in experimental bulk aerogels. The results are also of the same order of magnitude as experimental bulk aerogels, but they are consistently higher. By analyzing the pore size distribution on different simulation length scales, we show that such a disparity is due to finite sizes of pores that can be represented, where increasing simulation length scales lead to an increase in the largest pore size that can be modeled.