@article{larentzos_mansell_lisal_brennan_2018, title={Coarse-grain modelling using an equation-of-state many-body potential: application to fluid mixtures at high temperature and high pressure}, volume={116}, ISSN={["1362-3028"]}, DOI={10.1080/00268976.2018.1459920}, abstractNote={ABSTRACT A many-body, coarse-grain model, termed the product gas mixture model, is presented that accurately describes the thermodynamic behaviour of molecular mixtures. The coarse-grain model is developed by first approximating the mixture as a van der Waals one-fluid, and subsequently applying an exponential-6 equation-of-state to describe the forces and energies between particles in the spirit of the many-body model pioneered by Pagonabarraga and Frenkel. Isothermal dissipative particle dynamics simulations are carried out at thermochemical states that occur during decomposition of a prototypical energetic material, RDX (1,3,5-trinitro-1,3,5-triazinane). The product gas mixture model performance is assessed by comparing to an explicit-molecule model and a hard-core coarse-grain model based on the exponential-6 pair potential. Overall, the many-body, coarse-grain model is shown to accurately capture the structural and thermodynamic properties for the wide variety of thermochemical states considered, while the hard-core coarse-grain model cannot. The many-body, coarse-grain model overcomes the issues of transferability, scaling consistency and unphysical ordered phase behaviour that often afflict coarse-grain models. While specific thermochemical conditions related to RDX decomposition are considered, the results are generally applicable to the thermodynamic behaviour of other fluid mixtures at both moderate and extreme conditions. GRAPHICAL ABSTRACT}, number={21-22}, journal={MOLECULAR PHYSICS}, author={Larentzos, James P. and Mansell, J. Matthew and Lisal, Martin and Brennan, John K.}, year={2018}, pages={3271–3282} }
 @article{lisal_cosoli_smith_jain_gubbins_2008, title={Molecular-level simulations of chemical reaction equilibrium for nitric oxide dimerization reaction in disordered nanoporous carbons}, volume={272}, ISSN={["0378-3812"]}, DOI={10.1016/j.fluid.2008.07.015}, abstractNote={We report a molecular-level simulation study of the effects of confinement on chemical reaction equilibrium for the NO dimerization reaction, 2NO ⇌ (NO)2, in disordered nanoporous carbons. We use the Reaction Ensemble Monte Carlo (RxMC) method [W.R. Smith, B. Tříska, J. Chem. Phys. 100 (1994) 3019–3027; J.K. Johnson, A.Z. Panagiotopoulos, K.E. Gubbins, Mol. Phys. 81 (1994) 717–733] to investigate the effects of temperature and bulk pressure on the reaction conversion in three models of disordered nanoporous carbons obtained from sucrose in equilibrium with a vapor reservoir. Atomistic models of the carbons used [S.K. Jain, R.J.-M. Pellenq, J.P. Pikunic, K.E. Gubbins, Langmuir 22 (2006) 9942–9948] were constructed using the Hybrid Reverse Monte Carlo method, differing by the processing conditions used in the preparation of the corresponding real material. In addition to the RxMC simulations, we test conventional macroscopic adsorption models, such as the Langmuir–Freundlich, multisite Langmuir, vacancy solution and ideal adsorption solution models, in connection with the ideal-gas model for the vapor reservoir to model the reaction equilibrium. Pure fluid adsorption isotherms needed as input to the macroscopic models for mixture adsorption are generated using the Gibbs Ensemble Monte Carlo or Grand Canonical Monte Carlo simulations. We analyze the effects of the confinement, temperature and bulk pressure on the NO dimerization reaction equilibrium in terms of the reactive adsorption isotherms. The RxMC simulations and thermodynamic modeling show that the sucrose-based carbons substantially increase the conversion of NO to (NO)2 with respect to the vapor reservoir, where the conversion is less than a few percent.}, number={1-2}, journal={FLUID PHASE EQUILIBRIA}, author={Lisal, Martin and Cosoli, Paolo and Smith, William R. and Jain, Surendra K. and Gubbins, Keith E.}, year={2008}, month={Oct}, pages={18–31} }
 @article{turner_brennan_lisal_smith_johnson_gubbins_2008, title={Simulation of chemical reaction equilibria by the reaction ensemble Monte Carlo method: a review}, volume={34}, ISSN={["1029-0435"]}, DOI={10.1080/08927020801986564}, abstractNote={Understanding and predicting the equilibrium behaviour of chemically reacting systems in highly non-ideal environments is critical to many fields of science and technology, including solvation, nanoporous materials, catalyst design, combustion and propulsion science, shock physics and many more. A method with recent success in predicting the equilibrium behaviour of reactions under non-ideal conditions is the reaction ensemble Monte Carlo method (RxMC). RxMC has been applied to reactions confined in porous solids or near solid surfaces, reactions at high temperature and/or high pressure, reactions in solution and at phase interfaces. The only required information is a description of the intermolecular forces among the system molecules and standard free-energy data for the reacting components. Extensions of the original method include its combination with algorithms for systems involving phase equilibria, constant-enthalpy and constant-internal energy adiabatic conditions, a method to include reaction kinetics, a method to study the dynamics of reacting systems, and a mesoscale method to simulate long-chain molecule phase separation. This manuscript surveys the various applications and adaptations of the RxMC method to date. Additionally, the relationship between the RxMC method and other techniques that simulate chemical reaction behaviour is given, along with insight into some technical nuances not found in the pioneering papers.}, number={2}, journal={MOLECULAR SIMULATION}, author={Turner, C. Heath and Brennan, John K. and Lisal, Martin and Smith, William R. and Johnson, J. Karl and Gubbins, Keith E.}, year={2008}, pages={119–146} }
 @article{brennan_lisal_gubbins_rice_2004, title={Reaction ensemble molecular dynamics: Direct simulation of the dynamic equilibrium properties of chemically reacting mixtures}, volume={70}, ISSN={["1550-2376"]}, DOI={10.1103/physreve.70.061103}, abstractNote={A molecular simulation method to study the dynamics of chemically reacting mixtures is presented. The method uses a combination of stochastic and dynamic simulation steps, allowing for the simulation of both thermodynamic and transport properties. The method couples a molecular dynamics simulation cell (termed dynamic cell) to a reaction mixture simulation cell (termed control cell) that is formulated upon the reaction ensemble Monte Carlo (RxMC) method, hence the term reaction ensemble molecular dynamics. Thermodynamic and transport properties are calculated in the dynamic cell by using a constant-temperature molecular dynamics simulation method. RxMC forward and reverse reaction steps are performed in the control cell only, while molecular dynamics steps are performed in both the dynamic cell and the control cell. The control cell, which acts as a sink and source reservoir, is maintained at reaction equilibrium conditions via the RxMC algorithm. The reaction ensemble molecular dynamics method is analogous to the grand canonical ensemble molecular dynamics technique, while using some elements of the osmotic molecular dynamics method, and so simulates conditions that directly relate to real, open systems. The accuracy and stability of the method is assessed by considering the ammonia synthesis reaction N2 +3 H2 <-->2N H3 . It is shown to be a viable method for predicting the effects of nonideal environments on the dynamic properties (particularly diffusion) as well as reaction equilibria for chemically reacting mixtures.}, number={6}, journal={PHYSICAL REVIEW E}, author={Brennan, JK and Lisal, M and Gubbins, KE and Rice, BM}, year={2004}, month={Dec} }
 @article{lisal_hall_gubbins_panagiotopoulos_2003, title={Formation of Spherical Micelles in a supercritical Solvent: Lattice Monte Carlo simulation and multicomponent solution model}, volume={29}, ISSN={["0892-7022"]}, DOI={10.1080/0892702031000065809}, abstractNote={We modify Larson's lattice model [Larson, R.G., Scriven, L.E. and Davis, H.T. (1985). J. Chem. Phys. , 83 , 2411-2420] and use it to study formation of spherical micelles in a supercritical solvent by large-scale Monte Carlo (MC) simulations and by the multicomponent solution model. Carbon dioxide and perfluoroalkylpoly(ethylene oxide) serve as prototypes for the solvent and surfactant, respectively. Larson-model type parameters for carbon dioxide and perfluoroalkylpoly(ethylene oxide) are obtained using experimental values of critical parameters and solubility along with a modified Berthelot combining rule. We perform canonical MC simulations at a supercritical temperature and low surfactant concentrations, varying the number of surfactant head and tail segments and the solvent density. Various properties such as the critical micelle concentration, the aggregate size distribution and the size of the micelles is evaluated. The multicomponent solution model and the simulation results for the aggregate size distribution are then combined to determine the standard state chemical potential for the spherical micelles and the intermicellar interaction; we present a novel approach to model this standard state chemical potential. The implications of these results for the thermodynamics of the formation of the spherical micelles in supercritical solvents are explored.}, number={2}, journal={MOLECULAR SIMULATION}, author={Lisal, M and Hall, CK and Gubbins, KE and Panagiotopoulos, AZ}, year={2003}, pages={139–157} }
 @article{colina_olivera-fuentes_siperstein_lisal_gubbins_2003, title={Thermal properties of supercritical carbon dioxide by Monte Carlo simulations}, volume={29}, ISSN={["0892-7022"]}, DOI={10.1080/0892702031000117135}, abstractNote={We present simulation results for the volume expansivity, isothermal compressibility, isobaric heat capacity, Joule-Thomson coefficient and speed of sound for carbon dioxide (CO 2 ) in the supercritical region, using the fluctuation method based on Monte Carlo simulations in the isothermal-isobaric ensemble. We model CO 2 as a quadrupolar two-center Lennard-Jones fluid with potential parameters reported in the literature, derived from vapor-liquid equilibria (VLE) of CO 2 . We compare simulation results with an equation of state (EOS) for the two-center Lennard-Jones plus point quadrupole (2CLJQ) fluid and with a multiparametric EOS adjusted to represent CO 2 experimental data. It is concluded that the VLE-based parameters used to model CO 2 as a quadrupolar two-center Lennard-Jones fluid (both simulations and EOS) can be used with confidence for the prediction of thermodynamic properties, including those of industrial interest such as the speed of sound or Joule-Thomson coefficient, for CO 2 in the supercritical region, except in the extended critical region.}, number={6-7}, journal={MOLECULAR SIMULATION}, author={Colina, CM and Olivera-Fuentes, CG and Siperstein, FR and Lisal, M and Gubbins, KE}, year={2003}, month={Jun}, pages={405–412} }
 @article{colina_lisal_siperstein_gubbins_2002, title={Accurate CO2 Joule-Thomson inversion curve by molecular simulations}, volume={202}, ISSN={["0378-3812"]}, DOI={10.1016/S0378-3812(02)00126-7}, abstractNote={We present simulation of the Joule–Thomson inversion curve (JTIC) for carbon dioxide using two different approaches based on Monte Carlo (MC) simulations in the isothermal–isobaric ensemble. We model carbon dioxide using a two-center Lennard–Jones (LJ) plus point quadrupole moment (2CLJQ) potential. We show that a precision of four significant figures in ensemble averages of thermodynamic quantities of interest is needed to obtain accurately the JTIC. The agreement between the experimental data, Wagner equation of state (EOS) and our simulations results indicates that the 2CLJQ potential represents an excellent balance between simplicity and accuracy in modeling of carbon dioxide. Additionally, we calculate the JTIC using the BACKONE EOS (that uses the same intermolecular potential as in our simulations) and show that the BACKONE EOS performs very well in predicting the JTIC for carbon dioxide.}, number={2}, journal={FLUID PHASE EQUILIBRIA}, author={Colina, CM and Lisal, M and Siperstein, FR and Gubbins, KE}, year={2002}, month={Nov}, pages={253–262} }
 @article{lisal_hall_gubbins_panagiotopoulos_2002, title={Micellar behavior in supercritical solvent-surfactant systems from lattice Monte Carlo simulations}, volume={194}, DOI={10.1016/S0378-3812(01)00721-X}, abstractNote={We modify Larson’s lattice model [J. Chem. Phys. 83 (1985) 2411] and use it to study micellar behavior in supercritical solvent–surfactant systems by large-scale Monte Carlo (MC) simulations. Carbon dioxide and perfluoroalkylpoly(ethylene oxide) serve as prototypes for the solvent and surfactant, respectively. Larson-model type parameters for carbon dioxide and perfluoroalkylpoly(ethylene oxide) are obtained using experimental values for critical parameters and solubility along with a modified Berthelot mixing rule. We perform canonical MC simulations at a supercritical temperature varying the structure of the surfactant, the solvent density and the surfactant concentration. Various properties such as the critical micelle concentration, the overlap concentration, the aggregate size distribution, and the size and shape of the micelles are calculated. The implications of these results for the thermodynamics of micellar formation in supercritical solvents are examined.}, number={2002 Mar 30}, journal={Fluid Phase Equilibria}, author={Lisal, M. and Hall, C. K. and Gubbins, Keith and Panagiotopoulos, A. Z.}, year={2002}, pages={233–247} }