A new open system Monte Carlo procedure designed to overcome difficulties with insertion and deletion of molecules is introduced. The method utilizes gradual insertions and deletions of molecules through the use of a continuous coupling parameter and an adaptive bias potential. The method draws upon concepts from previous open system molecular dynamics and expanded ensemble Monte Carlo techniques and is applied to both the grand canonical and osmotic ensembles. It is shown to yield correct results for the volumetric properties of the Lennard-Jones fluid and water as well as the phase behavior of the CO2-ethanol binary system.

The solubility of water and carbon dioxide in the ionic liquid 1-n-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([hmim][Tf2N]) is computed using atomistic Monte Carlo simulations. A newly developed biasing algorithm is used to enable complete isotherms to be computed. In addition, a recently developed pairwise damped electrostatic potential calculation procedure is used to speed the calculations. The computed isotherms, Henry's Law constants, and partial molar enthalpies of absorption are all in quantitative agreement with available experimental data. The simulations predict that the excess molar volume of CO2/ionic liquid mixtures is large and negative. Analysis of ionic liquid conformations shows that the CO2 does not perturb the underlying liquid structure until very high CO2 concentrations are reached. At the highest CO2 concentrations, the alkyl chain on the cation stretches out slightly, and the distance between cation and anion centers of mass increases by about 1 angstroms. Water/ionic liquid mixtures have excess molar volumes that are also negative but much smaller in magnitude than those for the case of CO2.

Optimization of carbon nanotube bundles containing a distribution of nanotube diameters always gives structures with packing defects that form relatively large interstitial channels. Experimental data for CH4, Ar, and Xe adsorption are compared with simulations. Low coverage experimental isosteric heats are in excellent agreement with simulations of gases adsorbing into interstitial channels of defective nanotube bundles, whereas adsorption onto perfect bundles does not agree with experiments. Thus, an accurate description of adsorption on nanotube bundles must account for interstitial adsorption.

The continuous fractional component Monte Carlo (CFC MC) move (J Chem Theory Comput, 2007, 3, 1451) is extended to the Gibbs ensemble. The algorithm is validated against conventional simulations for the Lennard Jones fluid and a flexible water model. The method is also used to compute the vapor-liquid coexistence densities of a model for SO(2). The CFC molecule exchange move relies on the gradual insertion and deletion of molecules in conjunction with a self-adapting bias potential. As a result, the method does not require the formation of spontaneous voids in the dense fluid phase to be successful, leading to molecule exchange acceptance probabilities that are nearly independent of temperature. For example, over 1% of the vapor-liquid molecule exchange moves are successful for water at 280 K, whereas advanced rotational and configurational bias methods have success rates of less than 0.03%. The CFC move can be combined with other Monte Carlo moves to enable efficient simulation of dense strongly associating fluids that are to this point infeasible to model with standard methods.

Using a computational screening methodology, we predicted (AIChE J. 2008, 54, 2717) that the anion tris(pentafluoroethyl)trifluorophosphate ([FEP]) should increase the solubility of CO2 in ionic liquids (ILs) relative to a wide range of conventional anions. This prediction was confirmed experimentally. In this work, we develop a united-atom force field for the [FEP] anion and use the continuous fractional component Monte Carlo (CFC MC) method to predict CO2 absorption isotherms in 1-n-hexyl-3-methylimidazolium ([hmim]) [FEP] at 298.2 and 323.2 K and pressures up to 20.0 bar. The simulated isotherms overestimate the solubility of CO2 by about 20% but capture the experimental trends quite well. Additional Monte Carlo (MC) and molecular dynamics (MD) simulations are performed to study the mechanisms of CO2 absorption in [hmim][FEP] and [hmim][PF6]. The site-site radial distribution functions (RDFs) show that CO2 is highly organized around the [PF6] anion due to its symmetry and smaller size, while less ordered distributions were found around [FEP] and [hmim]. However, more CO2 can be found in the first coordination shell of [FEP] compared with [PF6]. The structures of ILs, illustrated by P-P radial distribution functions, change very little upon the addition of as much as 50 mol % CO2. An energetic analysis shows that the van der Waals interactions between CO2 and ILs are generally larger than electrostatic interactions.

The ability of simple classical force fields to predict the structure and density of ionic liquids is now well-established. However, it is less clear how accurate such force fields are for a range of other pure and mixture properties of ionic liquids. In this work, a single classical force field is used to compute a wide range of thermodynamic and transport properties for the ionic liquid 1-ethyl-3-methylimidazolium ethylsulfate ([emim][EtSO4]). In addition to liquid densities, the volumetric expansivity, heat capacity, enthalpy of vaporization, rotational relaxation time, self-diffusivity, shear viscosity, and thermal conductivity are computed at various temperatures for the pure ionic liquid. The density, excess molar volume, enthalpy of mixing, partial molar enthalpy, water solubility as a function of partial pressure, rotational relaxation time, self-diffusivity, shear viscosity, and thermal conductivity are also computed for mixtures that contain different concentrations of water at various temperatures. The agreement between simulations and experiment is fair for most properties, although deviations in enthalpy of mixing, viscosity, and self-diffusivity are often large. It is shown that much of the error for mixtures with water likely is due to neglect of the water polarizability, which results in too strong of an attraction between water and the [EtSO4] anion.

Monte Carlo simulations are carried out to compute the solubility of SO2, O2, and N2 in the ionic liquid 1-n-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([hmim][Tf2N]). Simulations are also used to compute the mixed gas isotherms for the mixtures CO2/O2, SO2/N2, and CO2/SO2. The pure gas isotherms agree well with available experimental data. For the mixtures CO2/O2 and SO2/N2, the simulations predict that the mixed gas solubilities are nearly ideal, with little enhancement or competition between the two solutes. This is contrary to published experimental studies, which found that in a gas mixture, CO2 enhances the solubility of the otherwise sparingly soluble O2 and that the poorly soluble N2 inhibits the solubility of the highly soluble SO2. For the SO2/CO2 mixture, it is found that the two gases absorb independently at low pressure but compete with one another at high pressure. An energetic analysis was performed for the different solutes in the ionic liquid. The van der Waals energy between the solutes and ionic liquid was greater than the electrostatic interactions, and the van der Waals interactions were roughly the same between the solutes and the two different ions. CO2 and SO2 interact more strongly with the anion than the cation due to stronger electrostatic interactions between the solute and the anion. N2 and O2 interact weakly with the ionic liquid and show little difference in interaction energy between the cation and anion. Regular solution theory (RST) was evaluated for its ability to predict pure and mixed gas isotherms. It was found that if RST was applied in a strictly predictive mode using experimentally derived parameters, solubilities of CO2 were underpredicted by a substantial margin.

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