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Bottom-Up Approach to the Coarse-Grained Surface Model: Effective Solid–Fluid Potentials for Adsorption on Heterogeneous Surfaces

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posted on 08.04.2019, 00:00 by Kaihang Shi, Erik E. Santiso, Keith E. Gubbins
Coarse-grained surface models with a low-dimension positional dependence have great advantages in simplifying the theoretical adsorption model and speeding up molecular simulations. In this work, we present a bottom-up strategy, developing a new two-dimensional (2D) coarse-grained surface model from the “bottom-level” atomistic model, for adsorption on highly heterogeneous surfaces with various types of defects. The corresponding effective solid–fluid potential consists of a 2D hard wall potential representing the structure of the surface and a one-dimensional (1D) effective area-weighted free-energy-averaged (AW-FEA) potential representing the energetic strength of the substrate–adsorbate interaction. Within the conventional free-energy-averaged (FEA) framework, an accessible-area-related parameter is introduced into the equation of the 1D effective solid–fluid potential, which allows us not only to obtain the energy information from the fully atomistic system but also to get the structural dependence of the potential on any geometric defect on the surface. Grand canonical Monte Carlo simulations are carried out for argon adsorption at 87.3 K to test the validity of the new 2D surface model against the fully atomistic system. We test four graphitic substrates with different levels of geometric roughness for the top layer, including the widely used reference solid substrate Cabot BP-280. The simulation results show that adding one more dimension to the traditional 1D surface model is essential for adsorption on the geometrically heterogeneous surfaces. In particular, the 2D surface model with the AW-FEA solid–fluid potential significantly improves the adsorption isotherm and density profile over the 1D surface model with the FEA solid–fluid potential over a wide range of pressure. The method to construct an effective solid–fluid potential for an energetically heterogeneous surface is also discussed.