Coarse grained force field for the molecular simulation of natural gases and condensates

AbstractThe atomistically-detailed molecular modelling of petroleum fluids is challenging, amongst other aspects, due to the very diverse multicomponent and asymmetric nature of the mixtures in question. Complicating matters further, the time scales for many important processes can be much larger than the current and foreseeable capacity of modern computers running fully-atomistic models. To overcome these limitations, a coarse grained (CG) model is proposed where some of the less-important degrees of freedom are safely integrated out, leaving as key parameters the average energy levels, the molecular conformations and the range of the Mie intermolecular potentials employed as the basis of the model. The parametrization is performed by using an analytical equation of state of the statistical associating fluid theory (SAFT) family to link the potential parameters to macroscopically observed thermophysical properties. The parameters found through this top-down approach are used directly in molecular dynamics simulations of multi-component multi-phase systems. The procedure is exemplified by calculating the phase envelope of the methane–decane binary and of two synthetic light condensate mixtures. A methodology based on the discrete expansion of a mixture is used to determine the bubble points of these latter mixtures, with an excellent agreement to experimental data. The model presented is entirely predictive and an abridged table of parameters for some fluids of interest is provided

SAFT-γ Force Field for the Simulation of Molecular Fluids 6. Binary and ternary mixtures comprising water, carbon dioxide, and n-alkanes

AbstractThe SAFT-γ coarse graining methodology (Avendaño et al., 2011) is used to develop force fields for the fluid-phase behaviour of binary and ternary mixtures comprising water, carbon dioxide, and n-alkanes. The effective intermolecular interactions between the coarse grained (CG) segments are directly related to macroscopic thermodynamic properties by means of the SAFT-γ equation of state for molecular segments represented with the Mie (generalised Lennard–Jones) intermolecular potential (Papaioannou et al., 2014). The unlike attractive interactions between the components of the mixtures are represented with a single adjustable parameter, which is shown to be transferable over a wide range of conditions. The SAFT-γ Mie CG force fields are used in molecular-dynamics simulations to predict the challenging (vapour+liquid) and (liquid+liquid) fluid-phase equilibria characterising these mixtures, and to study phenomena that are not accessible directly from the equation of state, such as the interfacial properties. The description of the fluid-phase equilibria and interfacial properties predicted with the SAFT-γ Mie force fields is in excellent agreement with the corresponding experimental data, and of comparable if not superior quality to that reported for the more sophisticated atomistic and united-atom models

Multiscale molecular simulations of the formation and structure of polyamide membranes created by interfacial polymerization

Large scale molecular simu lations to model the formation of polyamide membranes have been carried out using a procedure that mimics experimental interfacial polymerization of trimesoyl chloride (TMC) and metaphenylene diamine (MPD) monomers. A coarse - grained representation of the m onomers has been developed to facilitate these simulations, which captures essential features of the stereochemistry of the monomers and of amide bonding between them. Atomic models of the membranes are recreated from the final coarse - grained representatio ns. Consistent with earlier treatments, membranes are formed through the growth and aggregation of oligomer clusters. The membranes are inhomogeneous, displaying opposing gradients of trapped carboxyl and amine side groups, local density variations, and r egions where the density of amide bonding is reduced as a result of the aggregation process. We observe the interfacial polymerization reaction is self - limiting and the simulated membranes display a thickness of 5 – 10 nm. They also display a surface roughn ess of 1 – 4 nm. Comparisons are made with recently published experimental results on the structure and chemistry of these membranes and some interesting similarities and differences are found

Water droplet excess free energy determined by cluster mitosis using guided molecular dynamics

Atmospheric aerosols play a vital role in affecting climate by influencing the properties and lifetimes of clouds and precipitation. Understanding the underlying microscopic mechanisms involved in the nucleation of aerosol droplets from the vapour phase is therefore of great interest. One key thermodynamic quantity in nucleation is the excess free energy of cluster formation relative to that of the saturated vapour. In our current study, the excess free energy is extracted for clusters of pure water modelled with the TIP4P/2005 intermolecular potential using a method based on nonequilibrium molecular dynamics and the Jarzynski relation. The change in free energy associated with the "mitosis" or division of a cluster of N water molecules into two N/2 sub-clusters is evaluated. This methodology is an extension of the disassembly procedure used recently to calculate the excess free energy of argon clusters [H. Y. Tang and I. J. Ford, Phys. Rev. E 91, 023308 (2015)]. Our findings are compared to the corresponding excess free energies obtained from classical nucleation theory (CNT) as well as internally consistent classical theory (ICCT). The values of the excess free energy that we obtain with the mitosis method are consistent with CNT for large cluster sizes but for the smallest clusters, the results tend towards ICCT; for intermediate sized clusters, we obtain values between the ICCT and CNT predictions. Furthermore, the curvature-dependent surface tension which can be obtained by regarding the clusters as spherical droplets of bulk density is found to be a monotonically increasing function of cluster size for the studied range. The data are compared to other values reported in the literature, agreeing qualitatively with some but disagreeing with the values determined by Joswiak et al. [J. Phys. Chem. Lett. 4, 4267 (2013)] using a biased mitosis approach; an assessment of the differences is the main motivation for our current study

Extension of the SAFT-VR Mie EoS to model homonuclear rings and its parameterization based on the principle of corresponding states

The statistical associating fluid theory of variable range employing a Mie potential (SAFT-VR-Mie) proposed by Lafitte et al. (J. Chem Phys. 2013, 139, 154504) is one of the latest versions of the SAFT family. This particular version has been shown to have a remarkable capability to connect experimental determinations, theoretical calculations, and molecular simulations results. However, the theoretical development restricts the model to chains of beads connected in a linear fashion. In this work, the capabilities of the SAFT-VR Mie equation of state for modeling phase equilibria are extended for the case of planar ring compounds. This modification proposed replaces the Helmholtz energy of chain formation by an empirical contribution based on a parallelism to the second-order thermodynamic perturbation theory for hard sphere trimers. The proposed expression is given in terms of an extra parameter, χ, that depends on the number of beads, ms, and the geometry of the ring. The model is used to describe the phase equilibrium for planar ring compounds formed of Mie isotropic segments for the cases of ms equals to 3, 4, 5 (two configurations), and 7 (two configurations). The resulting molecular model is further parametrized, invoking a corresponding states principle resulting in sets of parameters that can be used indistinctively in theoretical calculations or in molecular simulations without any further refinements. The extent and performance of the methodology has been exemplified by predicting the phase equilibria and vapor pressure curves for aromatic hydrocarbons (benzene, hexafluorobenzene, toluene), heterocyclic molecules (2,5-dimethylfuran, sulfolane, tetrahydro-2H-pyran, tetrahydrofuran), and polycyclic aromatic hydrocarbons (naphthalene, pyrene, anthracene, pentacene, and coronene). An important aspect of the theory is that the parameters of the model can be used directly in molecular dynamics (MD) simulations to calculate equilibrium phase properties and interfacial tensions with an accuracy that rivals other coarse grained and united atom models, for example, liquid densities, are predicted, with a maximum absolute average deviation of 3% from both the theory and the MD simulations, while the interfacial tension is predicted, with a maximum absolute average of 8%. The extension to mixtures is exemplified by considering a binary system of hexane (chain fluid) and tetrahydro-2H-pyran (ring fluid)

SAFT-γ force field for the simulation of molecular fluids: 8. hetero-group coarse-grained models of perfluoroalkylalkanes assessed with new vapour-liquid interfacial tension data

The air-liquid interfacial behaviour of linear perfluoroalkylalkanes (PFAAs) is reported through a combined experimental and computer simulation study. The surface tensions of seven liquid PFAAs (perfluorobutylethane, F4H2; perfluorobutylpentane, F4H5; perfluorobutylhexane, F4H6, perfluorobutyloctane, F4H8; perfluorohexylethane, F6H2; perfluorohexylhexane, F6H6; and perfluorohexyloctane, F6H8) are experimentally determined over a wide temperature range (276 to 350 K). The corresponding surface thermodynamic properties and the critical temperatures of the studied compounds are estimated from the temperature dependence of the surface tension. Experimental density and vapour pressure data are employed to parameterize a generic heteronuclear coarse-grained intermolecular potential of the SAFT- γ family for PFAAs. The resulting force field is used in direct molecular dynamics simulations to predict with quantitative agreement the experimental tensions and to explore the conformations of the molecules in the interfacial region revealing a preferential alignment of the PFAA molecules towards the interface and an enrichment of the perfluoro-groups at the outer interface region

Understanding the experience of interactive art: Iamascope in Beta_space

This paper describes a study into the situated experience of interactive art. The study was conducted with audiences of the artwork Iamascope and is framed by the four categories of embodied experience that have been proposed by its artist Sidney Fels. The video-cued recall method we employed was shown to reveal rich detail about situated interactive art experience. The results provide a detailed account of how the categories of embodiment manifest themselves in audience experience and lead to the proposal of a blueprint for the trajectory of interaction produced by Iamascope which may be generalisable to other interactive artworks

Creating affective visualisations for a Physiologically interactive artwork

This paper describes an action research project based on the process of designing the visualisation of heart and breath rate data for the interactive artwork Cardiomorphologies. The project aimed to realise the affective goals of the artist as closely a

Experimental measurements and theoretical modeling of high-pressure mass densities and interfacial tensions of carbon dioxide + n-heptane + toluene and its carbon dioxide binary systems

Experimental determination and theoretical predictions of the isothermal (344.15 K) mass densities and interfacial tensions for the sys tem carbon dioxide (CO2) with heptol (n - heptane + toluene) mixtures varying liquid volume fraction compositions of toluene (0, 25, 50, 75, 100 % v/v) and over the pressure range 0.1 to 8 MPa are reported. Measurements are carried out on a high - pressure dev ice that includes a vibrating tube densimeter and a pendant drop tensiometer. Theoretical modeling of mass densities phase equilibria and interfacial properties (i.e., interfacial tension and interfacial concentration profiles) are performed by employing t he Square Gradient Theory using an extension of the Statistical Associating Fluid Theory equation of state that accounts for ring fluids. The experimental bulk phase equilibrium densities and interfacial tensions obtained are in very good agreement with th e theoretical predictions. Although there are no previous experimental data of these mixtures at the conditions explored herein, the results follow the same trends observed from experimental data at other conditions. The combination of experimental and mod eling approaches provides a route to simultaneously predict phase equilibrium and interfacial properties within acceptable statistical deviations. For the systems and conditions studied here, we observe that the phase equilibrium of the mixtures display z eotropic vapor - liquid equilibria with positive deviations from ideal behavior. The mass bulk densities behave ordinarily whereas the interfacial tensions decrease as the pressure or liquid mole fraction of CO2 increases and/or the ratio toluene/heptane dec reases. The interfacial concentration along the interfacial region exhibits a remarkable high excess adsorption of CO2, which increases with pressure and it is larger in n - heptane than in toluene. Toluene does not exhibit any special adsorption activity wh ereas n - heptane displays surface activity only at low pressure in a very narrow range for the case of CO2 + (25% n - heptane + 75% toluene) mixture

Working-fluid selection and performance investigation of a two-phase single-reciprocating-piston heat-conversion engine

We employ a validated first-order lumped dynamic model of the Up-THERM converter, a two-phase unsteady heat-engine that belongs to a class of innovative devices known as thermofluidic oscillators, which contain fewer moving parts than conventional engines and represent an attractive alternative for remote or off-grid power generation as well as waste-heat recovery. We investigate the performance the Up-THERM with respect to working-fluid selection for its prospective applications. An examination of relevant working-fluid thermodynamic properties reveals that the saturation pressure and vapour-phase density of the fluid play important roles in determining the performance of the Up-THERM – the device delivers a higher power output at high saturation pressures and has higher exergy efficiencies at low vapour-phase densities. Furthermore, working fluids with low critical temperatures, high critical pressures and exhibiting high values of reduced pressures and temperatures result in designs with high power outputs. For a nominal Up-THERM design corresponding to a target application with a heat-source temperature of 360 ◦C, water is compared with forty-five other pure working fluids. When maximizing the power output, R113 is identified as the optimal fluid, followed by i-hexane. Fluids such as siloxanes and heavier hydrocarbons are found to maximize the exergy and thermal efficiencies. The ability of the Up-THERM to convert heat over a range of heat-source temperatures is also investigated, and it is found that the device can deliver in excess of 10 kW when utilizing thermal energy at temperatures above 200 ◦C. Of all the working fluids considered here, ammonia, R245ca, R32, propene and butane feature prominently as optimal and versatile fluids delivering high power over a wide range of heat-source temperatures