@article{long_palmer_coasne_shi_sliwinska-bartkowiak_gubbins_2020, title={Reply to the 'Comment on "Pressure enhancement in carbon nanopores: a major confinement effect"' by D. van Dijk, Phys. Chem. Chem. Phys., 2020, 22, DOI: 10.1039/C9CP02890K}, volume={22}, ISSN={["1463-9084"]}, DOI={10.1039/c9cp04289j}, abstractNote={By calculating the unique effective tangential pressure and discussing recent evidence from experiment and simulations, we show that the high pressure and strong compression in adsorbed layers for wetting systems on carbon are significant.}, number={17}, journal={PHYSICAL CHEMISTRY CHEMICAL PHYSICS}, author={Long, Yun and Palmer, Jeremy C. and Coasne, Benoit and Shi, Kaihang and Sliwinska-Bartkowiak, Malgorzata and Gubbins, Keith E.}, year={2020}, month={May}, pages={9826–9830} }
 @article{long_palmer_coasne_sliwinska-bartkowiak_gubbins_2011, title={Pressure enhancement in carbon nanopores: a major confinement effect}, volume={13}, ISSN={["1463-9084"]}, DOI={10.1039/c1cp21407a}, abstractNote={Phenomena that only occur at high pressures in bulk phases are observed in nanopores because of a pressure enhancement effect.}, number={38}, journal={PHYSICAL CHEMISTRY CHEMICAL PHYSICS}, author={Long, Yun and Palmer, Jeremy C. and Coasne, Benoit and Sliwinska-Bartkowiak, Malgorzata and Gubbins, Keith E.}, year={2011}, pages={17163–17170} }
 @article{bhattacharya_coasne_hung_gubbins_2009, title={Modeling Micelle-Templated Mesoporous Material SBA-15: Atomistic Model and Gas Adsorption Studies}, volume={25}, ISSN={["0743-7463"]}, DOI={10.1021/la801560e}, abstractNote={We report the development of a realistic molecular model for mesoporous silica SBA-15, which includes both the large cylindrical mesopores and the smaller micropores in the pore walls. The methodology for modeling the SBA-15 structure involves molecular and mesoscale simulations combined with geometrical interpolation techniques. First, a mesoscale model is prepared by mimicking the synthesis process using lattice Monte Carlo simulations. The main physical features of this mesoscale pore model are then carved out of an atomistic silica block; both the mesopores and the micropores are incorporated from the mimetic simulations. The calculated pore size distribution, surface area, and simulated TEM images of the model structure are in good agreement with those obtained from experimental samples of SBA-15. We then investigate the adsorption of argon in this structure using Grand Canonical Monte Carlo (GCMC) simulations. The adsorption results for our SBA-15 model are compared with those for a similar model that does not include the micropores; we also compare with results obtained in a regular cylindrical pore. The simulated adsorption isotherm for the SBA-15 model shows semiquantitative agreement with the experimental isotherm for a SBA-15 sample having a similar pore size. We observe that the presence of the micropores leads to increased adsorption at low pressure compared to the case of a model without micropores in the pore walls. At higher pressures, for all models, the filling proceeds via the monolayer-multilayer adsorption on the mesopore surface followed by capillary condensation, which is mainly controlled by the mesopore diameter and is not influenced by the presence of the micropores.}, number={10}, journal={LANGMUIR}, author={Bhattacharya, Supriyo and Coasne, Benoit and Hung, Francisco R. and Gubbins, Keith E.}, year={2009}, month={May}, pages={5802–5813} }
 @inproceedings{hung_coasne_gubbins_siperstein_thommes_sliwinska-bartkowiak_2006, title={A Monte Carlo study of capillary condensation of krypton within realistic models of templated mesoporous silica materials}, volume={160}, DOI={10.1016/s0167-2991(07)80021-8}, abstractNote={We present a detailed simulation study of the hysteresis loop in conical pores and in cylindrical pores with periodic constrictions to understand how the non-uniformity of the pore diameter along the pore axis would affect the hysteresis loop. The shape and size of the loop in the conical pores (with and without closed ends) are modified by the cone angle because of the change in the curvature of the menisci at the pore ends. In periodically constricted cylindrical pores, the shape and size of the hysteresis loop are not significantly altered by the pore length or by the presence of a closed end because condensation and evaporation in this type of pore occur in the individual pore sections. Similar hysteresis loops have been found in experimental studies, suggesting that structures of the type modelled here occur in real materials.}, booktitle={Characterization of porous solids vii - proceedings of the 7th international symposium on the characterization of porous solids (cops-vii), aix-en-provence, france, 26-28 may 2005}, author={Hung, F. R. and Coasne, B. and Gubbins, Keith and Siperstein, F. R. and Thommes, M. and Sliwinska-Bartkowiak, M.}, year={2006}, pages={153–160} }
 @article{coasne_jain_gubbins_2007, title={Adsorption and dynamics of argon in porous carbons}, volume={141}, DOI={10.1141/epjst/e2007-00022-2}, journal={European Physical Journal. Special Topics}, author={Coasne, B. and Jain, S. K. and Gubbins, Keith}, year={2007}, pages={121–125} }
 @article{ratajczak_sliwinska-bartkowiak_coasne_gubbins_2007, title={An apparent critical point in binary mixtures of m-nitrotoluene with n-alkanes; experimental and simulation study}, volume={353}, ISSN={["1873-4812"]}, DOI={10.1016/j.jnoncrysol.2007.01.090}, abstractNote={We report a simulation study of the system m-nitrotoluene–n-decane, showing an apparent critical point, which lies in their metastable, experimentally inaccessible state, below their melting point, affecting physical and chemical properties of this systems in the stable liquid phase. The presence of the apparent critical point in this mixture has been experimentally observed by the non-linear dielectric effect (NDE) as an anomalous increase in the NDE values typical of critical concentrations. The phase diagrams of this mixture have evidenced that the system freezes in the homogenous phase and its melting point is higher than its critical temperature [M. Śliwińska-Bartkowiak, B. Szurkowski, T. Hilczer, Chem. Phys. Lett. 94 (1983) 609, M. Śliwińska-Bartkowiak, Ber. Bunsengess. Phys. Chem. 94 (1990) 64, M. Śliwińska-Bartkowiak, Phys. Lett. A 128 (1988) 84]. For such a system, we performed Monte Carlo simulations aimed at analyzing the kind of phase transition observed, and their conditions of their occurrence in a Lennard-Jones mixture. The enthalpy, configurational energy and radial distribution function have been estimated by the MC simulation method in the NPT system. Immiscibility conditions according to Hoheisel [M. Schoen, C. Hoheisel, Mol. Phys. 57 (1986) 65] approach have also been discussed.}, number={47-51}, journal={JOURNAL OF NON-CRYSTALLINE SOLIDS}, author={Ratajczak, B. and Sliwinska-Bartkowiak, M. and Coasne, B. and Gubbins, K. E.}, year={2007}, month={Dec}, pages={4565–4569} }
 @inbook{coasne_czwartos_gubbins_hung_sliwinska-bartkowiak_2007, title={Confinement effects on freezing of binary mixtures}, volume={160}, ISBN={9780444520227}, ISSN={0167-2991}, url={http://dx.doi.org/10.1016/s0167-2991(07)80086-3}, DOI={10.1016/s0167-2991(07)80086-3}, abstractNote={We report molecular simulations and experimental measurements of the freezing and melting of mixtures confined in nanopores. Dielectric relaxation spectroscopy was used to determine the experimental phase diagram of mixtures confined in activated carbon fibers. Grand Canonical Monte Carlo simulations combined with the parallel tempering technique were used to model the freezing of several Lennard - Jones mixtures in graphite slit pores. The effect of confinement is discussed for mixtures having a simple solid solution or an azeotropic solid - liquid phase diagram. We also investigate how the competition between the wall -fluid and fluid - fluid interactions affects the freezing temperature of the confined system. The structure of the crystal phase in the simulations is also investigated by means of positional and bond-orientational pair correlation functions and bond-order parameters.}, booktitle={Studies in Surface Science and Catalysis}, publisher={Elsevier}, author={Coasne, Benoit and Czwartos, Joanna and Gubbins, Keith E. and Hung, Francisco R. and Sliwinska-Bartkowiak, Malgorzata}, year={2007}, pages={667–674} }
 @article{coasne_jain_naamar_gubbins_2007, title={Freezing of argon in ordered and disordered porous carbon}, volume={76}, ISSN={["1098-0121"]}, DOI={10.1103/physrevb.76.085416}, abstractNote={We report a molecular simulation study on the freezing of argon within two models of activated porous carbons. Model A is a regular slit-shaped nanopore, which represents an ordered graphitic porous carbon with a single pore width. Model B is a realistic sample of a disordered porous carbon obtained from reverse Monte Carlo. The morphological pore shape and topological pore connectivity disorders of model B represent in a realistic way the complex porous structure of materials obtained after carbonization and activation of pure saccharose. This study is aimed at estimating how the effect of disorder of the porous material affects freezing and melting of simple adsorbates. Freezing of argon in the slit pore model conforms to the classical behavior for an adsorbate confined in a strongly attractive pore; the in-pore freezing temperature is higher than that of the bulk fluid, and the shift in freezing temperature increases with decreasing pore size. It is found that the two-dimensional crystal layers of argon within the slit pores have a hexagonal structure i.e., triangular symmetry. Freezing of argon within model B strongly departs from that observed for model A. No crystallization is observed for argon in the complex porosity of model B. Nevertheless the confined phase undergoes structural changes at a temperature T=115 K; this temperature is close to the freezing temperature found for the slit pore with width H=1.1 nm, which corresponds to the mean pore size in model B. For temperatures larger than T =115 K, the confined phase in model B exhibits a liquid-like behavior as revealed from pair correlation functions and bond-order parameters. On the other hand, the confined phase for T115 K has more shortrange order than the liquid phase but its overall behavior remains liquid-like. Our results indicate that the changes observed at T115 K are due 1 to the appearance in the confined phase of a small amount of crystal atoms and 2 to the fact that the fraction of liquid-like atoms having at least seven nearest neighbors reaches a plateau value of 80%. The results provide a basis for the interpretation of experiments such as NMR and scattering experiments on freezing in disordered porous materials.}, number={8}, journal={PHYSICAL REVIEW B}, author={Coasne, Benoit and Jain, Surendra K. and Naamar, Linda and Gubbins, Keith E.}, year={2007}, month={Aug} }
 @inproceedings{bhattacharya_coasne_hung_gubbins_2006, title={Modeling triblock surfactant templated mesoporous silicas (MCF and SBA-15): A mimetic simulation study}, volume={160}, DOI={10.1016/s0167-2991(07)80068-1}, abstractNote={We have developed models for templated mesoporous silicas such as Mesostructured Cellular Foams and SBA-15. The first part of our work elaborates the effect of oil concentration on the pore morphology of the triblock surfactant templated mesoporous materials. Our Lattice Monte Carlo simulations mimic the synthesis process by equilibrating a mixture of triblock surfactant, oil, water and silica at a constant temperature and density. With increasing oil concentration, we find the pore geometry to change according to the sequence: cylinders → lamellae → mesocells, which is in qualitative agreement with experimental results. In the second part of our work, we develop realistic atomistic models of the SBA-15 material, starting from the mesoscale model obtained from Lattice Monte Carlo simulations. Both the pore surface heterogeneity and the micropores are derived from the mimetic simulations. The simulated TEM and pore size distribution of the model qualitatively resemble the real material.}, booktitle={Characterization of porous solids vii - proceedings of the 7th international symposium on the characterization of porous solids (cops-vii), aix-en-provence, france, 26-28 may 2005}, author={Bhattacharya, S. and Coasne, B. and Hung, F. R. and Gubbins, Keith}, year={2006}, pages={527–534} }
 @article{coasne_gubbins_hung_jain_2006, title={Adsorption and structure of argon in activated porous carbons}, volume={32}, ISSN={["1029-0435"]}, DOI={10.1080/08927020600675707}, abstractNote={Molecular simulations are used to investigate the adsorption and structure of argon in ordered and disordered models of porous carbons. The ordered porous carbon (model A) is an assembly of regular slit pores of different sizes, while the disordered porous carbon (model B) is a structural model that reproduces the complex pore shape and pore connectivity of saccharose-based porous carbons. The same pore size distribution is used for models A and B so that we are able to estimate, for similar confinement effects, how the disorder of the porous material affects the adsorption and structure of the confined fluid. Adsorption of argon at 77.4 K in the two models is studied using Grand Canonical Monte Carlo simulations. The structure of the confined fluid is analyzed using crystalline bond order parameters and positional or bond orientational pair correlation functions. The filling pressure for the assembly of slit pores is much lower than that for the disordered porous carbon. It is also found that the isosteric heat of adsorption for the ordered porous model overestimates that for the disordered porous model. The results suggest that the agreement between models A and B would be improved if the same density of carbon atoms were used in these two models. Strong layering of Ar is observed at all pressures for model A. The confined phase is composed of liquid-like layers at low-pressures, which crystallize into well-defined hexagonal 2D crystals after complete filling of the pores. The structure of argon in the disordered porous carbon strongly departs from that in the slit pore model. Although its structure remains liquid-like overall, argon confined in model B is composed of both crystalline clusters and amorphous (solid or liquid) nano-domains.}, number={7}, journal={MOLECULAR SIMULATION}, author={Coasne, Benoit and Gubbins, Keith E. and Hung, Francisco R. and Jain, Surendra K.}, year={2006}, month={Jun}, pages={557–566} }
 @article{coasne_jain_gubbins_2006, title={Adsorption, structure and dynamics of fluids in ordered and disordered models of porous carbons}, volume={104}, ISSN={["1362-3028"]}, DOI={10.1080/00268970601012736}, abstractNote={Grand Canonical Monte Carlo and Molecular Dynamics simulations are used to investigate the adsorption and dynamics of argon in ordered and disordered models of porous carbons. The ordered porous carbon (model A) is a regular slit pore made up of graphene sheets. The disordered porous carbon (model B) is a structural model that reproduces the morphological (pore shape) and topological (pore connectivity) disorders of saccharose-based porous carbons. Three pore widths, H = 7, 11, and 15 Å, are selected for model A; they correspond to the smaller, mean, and larger pore sizes of model B. The filling pressures for the graphite slit pores are lower than those for the disordered porous carbon. It is also found that model A is not able to capture the behaviour of the isosteric heat of adsorption of model B. For all pressures, the confined phase in model A is composed of well-defined layers, which crystallize into hexagonal 2D crystals after complete filling of the pores. In contrast, the structure of argon in the disordered porous carbon remains liquid-like overall. It is also found that the slit pore model cannot reproduce the dynamics of argon in the disordered porous carbon. While the self-diffusivity of argon in model A decreases with increasing loading, it exhibits a maximum for model B. Such a non-monotonic behaviour of the self-diffusivity for the disordered porous carbon can be explained by the surface (energetic) heterogeneities of the material.}, number={22-24}, journal={MOLECULAR PHYSICS}, author={Coasne, B. and Jain, S. K. and Gubbins, K. E.}, year={2006}, pages={3491–3499} }
 @misc{alba-simionesco_coasne_dosseh_dudziak_gubbins_radhakrishnan_sliwinska-bartkowiak_2006, title={Effects of confinement on freezing and melting}, volume={18}, ISSN={["1361-648X"]}, DOI={10.1088/0953-8984/18/6/R01}, abstractNote={We present a review of experimental, theoretical, and molecular simulation studies of confinement effects on freezing and melting. We consider both simple and more complex adsorbates that are confined in various environments (slit or cylindrical pores and also disordered porous materials). The most commonly used molecular simulation, theoretical and experimental methods are first presented. We also provide a brief description of the most widely used porous materials. The current state of knowledge on the effects of confinement on structure and freezing temperature, and the appearance of new surface-driven and confinement-driven phases are then discussed. We also address how confinement affects the glass transition.}, number={6}, journal={JOURNAL OF PHYSICS-CONDENSED MATTER}, author={Alba-Simionesco, C. and Coasne, B. and Dosseh, G. and Dudziak, G. and Gubbins, K. E. and Radhakrishnan, R. and Sliwinska-Bartkowiak, M.}, year={2006}, month={Feb}, pages={R15–R68} }
 @article{coasne_jain_gubbins_2006, title={Freezing of fluids confined in a disordered nanoporous structure}, volume={97}, number={10}, journal={Physical Review Letters}, author={Coasne, B. and Jain, S. K. and Gubbins, K. E.}, year={2006} }
 @article{coasne_hung_pellenq_siperstein_gubbins_2006, title={Adsorption of Simple Gases in MCM-41 Materials: The Role of Surface Roughness}, volume={22}, ISSN={["0743-7463"]}, DOI={10.1021/la051676g}, abstractNote={This paper reports the development and testing of atomistic models of silica MCM-41 pores. Model A is a regular cylindrical pore having a constant section. Model B has a surface disorder that reproduces the morphological features of a pore obtained from an on-lattice simulation that mimics the synthesis process of MCM-41 materials. Both models are generated using a similar procedure, which consists of carving the pore out of an atomistic silica block. The differences between the two models are analyzed in terms of small angle neutron scattering spectra as well as adsorption isotherms and isosteric heat curves for Ar at 87 K and Xe at 195 K. As expected for capillary condensation in regular nanopores, the Ar and Xe adsorption/desorption cycles for model A exhibit a large hysteresis loop having a symmetrical shape, i.e., with parallel adsorption and desorption branches. The features of the adsorption isotherms for model B strongly depart from those observed for model A. Both the Ar and Xe adsorption branches for model B correspond to a quasicontinuous pore filling that involves coexistence within the pore of liquid bridges and gas nanobubbles. As in the case of model A, the Ar adsorption isotherm for model B exhibits a significant hysteresis loop; however, the shape of the loop is asymmetrical with a desorption branch much steeper than the adsorption branch. In contrast, the adsorption/desorption cycle for Xe in model B is quasicontinuous and quasireversible. Comparison with adsorption and neutron scattering experiments suggests that model B is too rough at the molecular scale but reproduces reasonably the surface disorder of real MCM-41 at larger length scales. In contrast, model A is smooth at small length scales in agreement with experiments but seems to be too ordered at larger length scales.}, number={1}, journal={LANGMUIR}, author={Coasne, B and Hung, FR and Pellenq, RJM and Siperstein, FR and Gubbins, KE}, year={2006}, month={Jan}, pages={194–202} }
 @article{coasne_gubbins_pellenq_2005, title={Domain theory for capillary condensation hysteresis}, volume={72}, ISSN={["1098-0121"]}, DOI={10.1103/physrevb.72.024304}, abstractNote={We discuss how the original domain theory for capillary condensation hysteresis D. H. Everett, The Solid– Gas Interface, Vol. 2 Marcel Dekker, New York, 1967, pp. 1055–1113 must be modified to account for the presence of the film adsorbed at the pore surface. We show that the original predictions scanning behavior, congruence are not valid unless the existence of the adsorbed film is neglected or the dependence of its thickness on the pressure is neglected. We also calculate the scanning curves and subloops that are expected for an assembly of pores having either a regular or irregular nonconstant section. These predictions over the scanning behavior within capillary condensation hysteresis can be used to check whether real materials are made up of independent pores or not. Our results are discussed in the light of experiments and density functional theory calculations for adsorption in porous media. I. INTRODUCTION Adsorption isotherms in mesoporous materials pore size in the range 2–1 0 nm usually exhibit a sharp increase of the adsorbed amount at a pressure below the bulk saturation pressure of the fluid. Such an increase corresponds to the capillary condensation of the fluid confined within the porous solid. In most systems, this phenomenon is accompanied with a large and reproducible hysteresis loop. 1–3 Experimental hysteresis loops are either symmetrical with quasiparallel adsorption/desorption branches type H1 or asymmetrical with a desorption branch much steeper than the adsorption branch type H2. 4 It is generally believed that the shape of the hysteresis loop is related to the absence or presence of connected pores in the porous material. The following International Union of Pure and Applied Chemists IUPAC classification has been proposed. 4 Type H1 hysteresis is usually interpreted as the signature of a material made up of unconnected pores. In this case, theoretical works based on density functional theory DFT, 5,6 lattice gas models, 7 as well as molecular simulations 8,9 suggest that the hysteresis loop is a van der Waals loop of the confined system, i.e., an intrinsic property of the confined fluid. Such an interpretation is usually invoked to explain symmetrical hysteresis loops that are observed for MCM-41 and SBA-15}, number={2}, journal={PHYSICAL REVIEW B}, author={Coasne, B and Gubbins, KE and Pellenq, RJM}, year={2005}, month={Jul} }
 @article{czwartos_coasne_gubbins_hung_sliwinska-bartkowiak_2005, title={Freezing and melting of azeotropic mixtures confined in nanopores: experiment and molecular simulation}, volume={103}, ISSN={["1362-3028"]}, DOI={10.1080/00268970500200101}, abstractNote={The paper reports on a qualitative comparison between experimental measurements and molecular simulations of the freezing and melting of azeotropic mixtures confined in nanoporous materials. Dielectric relaxation spectroscopy was used to determine the experimental solid/liquid phase diagram of CCl4/C6H12 mixtures confined in activated carbon fibres. Grand Canonical Monte Carlo simulations combined with the parallel tempering technique were used to model the freezing of the azeotropic Lennard–Jones mixture Ar/CH4 in a graphite slit pore. The structure of the crystal phase in the simulations is investigated by means of positional and bond-orientational pair correlation functions and appropriate bond-order parameters. Both simulations and experiments show that the phase diagram of the confined mixture is of the same type as that for the bulk, but the solid/liquid coexistence lines are located at higher temperatures. The effect of confinement and of the wall/fluid interaction on the location of the azeotrope is discussed.}, number={21-23}, journal={MOLECULAR PHYSICS}, author={Czwartos, J and Coasne, B and Gubbins, KE and Hung, FR and Sliwinska-Bartkowiak, M}, year={2005}, pages={3103–3113} }
 @article{coasne_czwartos_gubbins_hung_sliwinska-bartkowiak_2005, title={Freezing of mixtures confined in a slit nanopore}, volume={11}, ISSN={["1572-8757"]}, DOI={10.1007/s10450-005-5941-4}, abstractNote={We report a Grand Canonical Monte Carlo study of the freezing/melting of Lennard-Jones A/B mixtures confined in a slit pore (H = 1.44 nm). The fluid/fluid interactions are chosen to model A = Ar and B = Kr. Fluid/wall interaction parameters are chosen so that the ratio of the wall/fluid to the fluid/fluid interactions for Kr and Ar is larger and smaller than 1, respectively. We find that the phase diagram of the confined mixture is of the same type than that for the bulk. The freezing temperature of confined mixtures rich in Kr is larger than the bulk. In contrast, we observe a decrease of the freezing temperature for mixtures rich in Ar. The confined crystal has a hexagonal structure (triangular symmetry), except for pure Ar where a square structure is observed.}, number={Suppl. 1}, journal={ADSORPTION-JOURNAL OF THE INTERNATIONAL ADSORPTION SOCIETY}, author={Coasne, B and Czwartos, J and Gubbins, KE and Hung, FR and Sliwinska-Bartkowiak, M}, year={2005}, pages={301–306} }
 @article{hung_coasne_santiso_gubbins_siperstein_sliwinska-bartkowiak_2005, title={Molecular modeling of freezing of simple fluids confined within carbon nanotubes}, volume={122}, ISSN={["1089-7690"]}, DOI={10.1063/1.1881072}, abstractNote={We report Monte Carlo simulation results for freezing of Lennard-Jones carbon tetrachloride confined within model multiwalled carbon nanotubes of different diameters. The structure and thermodynamic stability of the confined phases, as well as the transition temperatures, were determined from parallel tempering grand canonical Monte Carlo simulations and free-energy calculations. The simulations show that the adsorbate forms concentric molecular layers that solidify into defective quasi-two-dimensional hexagonal crystals. Freezing in such concentric layers occurs via intermediate phases that show remnants of hexatic behavior, similar to the freezing mechanism observed for slit pores in previous works. The adsorbate molecules in the inner regions of the pore also exhibit changes in their properties upon reduction of temperature. The structural changes in the different regions of adsorbate occur at temperatures above or below the bulk freezing point, depending on pore diameter and distance of the adsorbate molecules from the pore wall. The simulations show evidence of a rich phase behavior in confinement; a number of phases, some of them inhomogeneous, were observed for the pore sizes considered. The multiple transition temperatures obtained from the simulations were found to be in good agreement with recent dielectric relaxation spectroscopy experiments for CCl(4) confined within multiwalled carbon nanotubes.}, number={14}, journal={JOURNAL OF CHEMICAL PHYSICS}, author={Hung, FR and Coasne, B and Santiso, EE and Gubbins, KE and Siperstein, FR and Sliwinska-Bartkowiak, M}, year={2005}, month={Apr} }
 @article{coasne_gubbins_pellenq_2005, title={Temperature effect on adsorption/desorption isotherms for a simple fluid confined within various nanopores}, volume={11}, ISSN={["1572-8757"]}, DOI={10.1007/s10450-005-5939-y}, abstractNote={We report a Grand Canonical Monte Carlo study of the temperature dependence of adsorption/desorption hysteresis for porous matrices having different morphologies and topologies. We aim at gaining some insights on the concept of critical hysteresis temperature, T cc , defined as the temperature at which the hysteresis loop disappears. Simulated T cc for cylindrical, ellipsoidal, and constricted pores follow the experimental scaling law established for MCM-41 silica materials. In contrast, T cc for Vycor samples with a largest pore size ~2.5 nm and 5.0 nm obey a different relationship, in qualitative agreement with experiments.}, number={Suppl. 1}, journal={ADSORPTION-JOURNAL OF THE INTERNATIONAL ADSORPTION SOCIETY}, author={Coasne, B and Gubbins, KE and Pellenq, RJM}, year={2005}, pages={289–294} }
 @article{coasne_gubbins_pellenq_2004, title={A grand canonical Monte Carlo study of adsorption and capillary phenomena in nanopores of various morphologies and topologies: Testing the BET and BJH characterization methods}, volume={21}, ISSN={["1521-4117"]}, DOI={10.1002/ppsc.200400928}, abstractNote={AbstractWe report a Grand Canonical Monte Carlo simulation study of Ar adsorption at 77 K in silica nanopores having various morphologies/topologies. Both the morphological and topological disorders are shown to significantly affect the capillary condensation phenomenon. In the case of an ellipsoidal pore, we observe that the filling mechanism is similar to that of a cylindrical pore having the same section area but with a lower condensation pressure. We show that the adsorption/desorption hysteresis loop is asymmetrical for the pore with constrictions while it is symmetrical for the regular cylindrical pore. Moreover, the Ar adsorption isotherm for the constricted pore reproduces the main features of that for the fully disordered Vycor‐like porous matrix. The results for the different pore geometries (having no direct interface with the gas reservoir) indicate that the desorption occurs through cavitation at a pressure driven by the smallest void size. We also consider the validity of the BET and BJH methods for the different porous matrices. Except for the Vycor‐like matrix, the BET surface assessed from Ar adsorption isotherm at 77 K always significantly overestimates the intrinsic surface of the pore (even for a planar surface). The disagreement between the BET surface and the geometrical surface is found to increase as the confinement increases (cylindrical pore) and/or the shape of the pore becomes asymmetrical (ellipsoidal pore). Interestingly, the best agreement between the BET and the geometrical surface is found in the case of the pore with a constriction, i.e. a system that exhibits a surface with both negative and positive curvature regions. This idea is supported by the results for the Vycor‐like matrix, which has a distorted surface (many negative curvature regions combined with positive curvature regions): for this disordered porous matrix, the BET surface is found to underestimate the intrinsic surface. Finally, we show that the pore size determined using the BJH method always underestimates the pore size, in agreement with previous experimental and simulation studies.}, number={2}, journal={PARTICLE & PARTICLE SYSTEMS CHARACTERIZATION}, author={Coasne, B and Gubbins, KE and Pellenq, RJM}, year={2004}, month={Aug}, pages={149–160} }
 @article{coasne_czwartos_gubbins_hung_sliwinska-bartkowiak_2004, title={Freezing and melting of binary mixtures confined in a nanopore}, volume={102}, ISSN={["1362-3028"]}, DOI={10.1080/00268970412331292678}, abstractNote={This paper reports on a Grand Canonical Monte Carlo study of the freezing and melting of Lennard–Jones Ar/Kr mixtures confined in a slit pore composed of two strongly attractive structureless walls. For all molar compositions and temperatures, the pore, which has a width of 1.44 nm, accommodates two contact layers and one inner layer. Different wall/fluid interactions are considered, corresponding to pore walls that have a larger affinity for either Ar or Kr. The solid/liquid phase diagram of the confined mixture is determined and results compared with data for the bulk mixture. The structure of the confined mixture is studied using 2D order parameters and both positional g(r) and bond orientational G6(r) pair correlation functions. It is found that in the confined solid phase, both the contact and inner layers have a hexagonal crystal structure. It is shown that the freezing temperature of the Ar/Kr confined mixture is higher than the bulk freezing point for all molar compositions. Also, it is found that the freezing temperature becomes larger as the ratio α of the wall/fluid to the fluid/fluid interactions increases, in agreement with previous simulation studies on pure substances confined in nanopores. In the case of pore walls having a stronger affinity for Kr atoms (ε Ar/W<ε Kr/W), it is observed that both the contact and inner layers of the confined mixture undergo, at the same temperature, a transition from the liquid phase to the crystal phase. The freezing of Ar/Kr mixtures confined between the walls having a stronger affinity for Ar (ε Ar/W > ε Kr/W) is more complex: for Kr molar concentration lower than 0.35, we observe the presence of an intermediate state between all layers being 2D hexagonal crystals and all the layers being liquid. This intermediate state consists of a crystalline contact layer and a liquid-like inner layer. It is also shown that the qualitative variations of the increase of freezing temperature with the molar composition depend on the affinity of the pore wall for the different components. These results confirm that, in addition to the parameter α the ratio of the wall/fluid interactions for the two species, η=ϵAr/W/ϵKr/W, is a key variable in determining the freezing and melting behaviour of the confined mixture.}, number={19-20}, journal={MOLECULAR PHYSICS}, author={Coasne, B and Czwartos, J and Gubbins, KE and Hung, FR and Sliwinska-Bartkowiak, M}, year={2004}, month={Oct}, pages={2149–2163} }