Local density dependent potentials for an underlying van der Waals equation of state: A simulation and density functional theory analysis.

There is an ever increasing use of local density dependent potentials in the mesoscale modeling of complex fluids. Questions remain, though, about the dependence of the thermodynamic and structural properties of such systems on the cutoff distance used to calculate these local densities. These questions are particularly acute when it comes to the stability and structure of the vapor/liquid interface. In this article, we consider local density dependent potentials derived from an underlying van der Waals equation of state. We use simulation and density functional theory to examine how the bulk thermodynamic and interfacial properties vary with the cutoff distance, rc, used to calculate the local densities. We show quantitatively how the simulation results for bulk thermodynamic properties and vapor-liquid equilibrium approach the van der Waals limit as rc increases and demonstrate a scaling law for the radial distribution function in the large rc limit. We show that the vapor-liquid interface is stable with a well-defined surface tension and that the interfacial density profile is oscillatory, except for temperatures close to critical. Finally, we show that in the large rc limit, the interfacial tension is proportional to rc and, therefore, unlike the bulk thermodynamic properties, does not approach a constant value as rc increases. We believe that these results give new insights into the properties of local density dependent potentials, in particular their unusual interfacial behavior, which is relevant for modeling complex fluids in soft matter.

[1]  C. Amador,et al.  A many-body dissipative particle dynamics parametrisation scheme to study behaviour at air-water interfaces. , 2023, Soft matter.

[2]  W. Noid Perspective: Advances, Challenges, and Insight for Predictive Coarse-Grained Models. , 2023, The journal of physical chemistry. B.

[3]  Shuo Chen,et al.  A review of many-body dissipative particle dynamics (MDPD): Theoretical models and its applications , 2021, Physics of Fluids.

[4]  Richard L. Anderson,et al.  Recent advances in particle-based simulation of surfactants , 2020 .

[5]  Michael R DeLyser,et al.  Analysis of local density potentials. , 2019, The Journal of chemical physics.

[6]  James P. Larentzos,et al.  Generalised dissipative particle dynamics with energy conservation: density- and temperature-dependent potentials. , 2019, Physical chemistry chemical physics : PCCP.

[7]  Li-jun Yang,et al.  Hypernetted-chain-like closure of Ornstein-Zernike equation in multibody dissipative particle dynamics. , 2017, Physical review. E.

[8]  Shuo Chen,et al.  Dynamical behaviors of droplet impingement and spreading on chemically heterogeneous surfaces , 2017 .

[9]  P. Español,et al.  Perspective: Dissipative particle dynamics. , 2016, The Journal of chemical physics.

[10]  P. Peralta,et al.  A pressure-transferable coarse-grained potential for modeling the shock Hugoniot of polyethylene. , 2016, The Journal of chemical physics.

[11]  Tanmoy Sanyal,et al.  Coarse-grained models using local-density potentials optimized with the relative entropy: Application to implicit solvation. , 2016, The Journal of chemical physics.

[12]  Shuo Chen,et al.  Droplets motion on chemically/topographically heterogeneous surfaces , 2016 .

[13]  J. Maia,et al.  Generalized mapping of multi-body dissipative particle dynamics onto fluid compressibility and the Flory-Huggins theory. , 2015, The Journal of chemical physics.

[14]  James P. Larentzos,et al.  Coarse-Grain Model Simulations of Nonequilibrium Dynamics in Heterogeneous Materials. , 2014, The journal of physical chemistry letters.

[15]  Zhen Li,et al.  Three dimensional flow structures in a moving droplet on substrate: A dissipative particle dynamics study , 2013 .

[16]  P. B. Warren No-go theorem in many-body dissipative particle dynamics. , 2013, Physical review. E, Statistical, nonlinear, and soft matter physics.

[17]  Aziz Ghoufi,et al.  Recent advances in Many Body Dissipative Particles Dynamics simulations of liquid-vapor interfaces , 2013, The European physical journal. E, Soft matter.

[18]  A. Ghoufi,et al.  Mesoscale modeling of the water liquid-vapor interface: a surface tension calculation. , 2011, Physical review. E, Statistical, nonlinear, and soft matter physics.

[19]  A. Ghoufi,et al.  Calculation of the surface tension from multibody dissipative particle dynamics and Monte Carlo methods. , 2010, Physical review. E, Statistical, nonlinear, and soft matter physics.

[20]  José Mario Martínez,et al.  PACKMOL: A package for building initial configurations for molecular dynamics simulations , 2009, J. Comput. Chem..

[21]  G. Rutledge,et al.  Coarse-grained, density dependent implicit solvent model reliably reproduces behavior of a model surfactant system. , 2009, The Journal of chemical physics.

[22]  I. Pagonabarraga,et al.  Modelling capillary phenomena at a mesoscale: From simple to complex fluids ☆ , 2008 .

[23]  M. Klein,et al.  Large-Scale Molecular Dynamics Simulations of Self-Assembling Systems , 2008, Science.

[24]  J. Abraham,et al.  Simulations of liquid nanocylinder breakup with dissipative particle dynamics. , 2008, Physical review. E, Statistical, nonlinear, and soft matter physics.

[25]  Gregory C Rutledge,et al.  A novel algorithm for creating coarse-grained, density dependent implicit solvent models. , 2008, The Journal of chemical physics.

[26]  Carlos Vega,et al.  Determination of the melting point of hard spheres from direct coexistence simulation methods. , 2008, The Journal of chemical physics.

[27]  I. Pagonabarraga,et al.  Density dependent potentials: structure and thermodynamics. , 2007, The Journal of chemical physics.

[28]  I Pagonabarraga,et al.  A mesoscopic model for (de)wetting , 2006, The European physical journal. E, Soft matter.

[29]  Hans Hasse,et al.  Comprehensive study of the vapour–liquid coexistence of the truncated and shifted Lennard–Jones fluid including planar and spherical interface properties , 2006 .

[30]  J. Abraham,et al.  A Dissipative Particle Dynamics model for two-phase flows , 2005 .

[31]  P. Tarazona,et al.  Intrinsic profiles beyond the capillary wave theory: a Monte Carlo study. , 2003, Physical review letters.

[32]  P. B. Warren,et al.  Vapor-liquid coexistence in many-body dissipative particle dynamics. , 2003, Physical review. E, Statistical, nonlinear, and soft matter physics.

[33]  D. Frenkel,et al.  Continuous freezing in three dimensions. , 2003, Physical review letters.

[34]  Maj Thijs Michels,et al.  Thermodynamic consistency in dissipative particle dynamics simulations of strongly nonideal liquids and liquid mixtures , 2002 .

[35]  I. Pagonabarraga,et al.  Dissipative particle dynamics for interacting systems , 2001, cond-mat/0105075.

[36]  P. B. Warren Hydrodynamic bubble coarsening in off-critical vapor-liquid phase separation. , 2001, Physical review letters.

[37]  A. Louis Effective potentials for polymers and colloids: beyond the van der Waals picture of fluids? , 2001, Philosophical Transactions of the Royal Society of London. Series A: Mathematical, Physical and Engineering Sciences.

[38]  Hansen,et al.  Mean-field fluid behavior of the gaussian core model , 2000, Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics.

[39]  John C. Shelley,et al.  Computer simulation of surfactant solutions , 2000 .

[40]  J. Alejandre,et al.  Computer simulations of liquid/vapor interface in Lennard-Jones fluids: Some questions and answers , 1999 .

[41]  P. B. Warren,et al.  DISSIPATIVE PARTICLE DYNAMICS : BRIDGING THE GAP BETWEEN ATOMISTIC AND MESOSCOPIC SIMULATION , 1997 .

[42]  R. Evans The nature of the liquid-vapour interface and other topics in the statistical mechanics of non-uniform, classical fluids , 1979 .

[43]  M. Fisher,et al.  Decay of Correlations in Linear Systems , 1969 .

[44]  A. Siegert,et al.  Statistical Mechanics of Hard‐Particle Systems , 1968 .

[45]  B. Widom,et al.  Some Topics in the Theory of Fluids , 1963 .

[46]  J. Kirkwood,et al.  Statistical Mechanics of Liquid Solutions. , 1936 .

[47]  C. Avendaño,et al.  Coarse‐grained methods for polymeric materials: enthalpy‐ and entropy‐driven models , 2014 .

[48]  D. Hoyle,et al.  Asymptotic decay of correlations in liquids and their mixtures , 1994 .