We address the question of how reducing the number of degrees of freedom modifies the interfacial thermodynamic properties of heterogeneous solid-liquid systems. We consider the example of n-hexane interacting with multi-layer graphene which we model both with fully atomistic and coarse-grained (CG) models. The CG models are obtained by means of the conditional reversible work (CRW) method. The interfacial thermodynamics of these models is characterized by the solid-liquid work of adhesion WSL calculated by means of the dry-surface methodology through molecular dynamics simulations. We find that the CRW potentials lead to values of WSL that are larger than the atomistic ones. Clear understanding of the relationship between the structure of n-hexane in the vicinity of the surface and WSL is elucidated through a detailed study of the energy and entropy components of WSL. We highlight the crucial role played by the solid-liquid energy fluctuations. Our approach suggests that CG potentials should be designed in such a way that they preserve the range of solid-liquid interaction energies, but also their fluctuations in order to preserve the reference atomistic value of WSL. Our study thus opens perspectives into deriving CG interaction potentials that preserve the thermodynamics of solid-liquid contacts and will find application in studies that intend to address materials driven by interfaces.

Lipid membranes are indispensable to life, and they regulate countless cellular processes. To investigate the properties of membranes under controlled conditions, numerous reconstitution methods have been developed over the last few decades. Several of these methods result in the formation of lipid bilayers containing residual hydrophobic molecules between the two monolayers. These contaminants might alter membrane properties, including bilayer thickness, that is usually inferred from measurements of membrane capacitance assuming a simple slab model. However, recent measurements on solvent-free bilayers raised significant questions on the reliability of this approach. To reconcile the observed discrepancies, we developed a protocol to predict membrane capacitance from the dielectric profile of lipid bilayers computed from molecular dynamics simulations. Our methodology shows excellent agreement against available data on solvent-free noncharged bilayers, and it confirms that the uniform slab model is a reliable approximation from which to infer membrane capacitance. We find that the effective electrical thickness contributing to membrane capacitance is different from the hydrophobic thickness inferred from X-ray scattering form factors. We apply our model to estimate the concentration of residual solvent in reconstituted systems, and we propose that our protocol could be used to infer membrane properties in the presence of hydrophobic solvents.

Molecular dynamics simulations have been performed to investigate the mechanism of thermal energy transport at the interface between n-heneicosane in solid and liquid phases and few-layer graphene at different temperatures under two heating modes (in the "heat-matrix" mode, heat is flowing from the heated heneicosane molecules to the cooled ones through the graphene layers and in the "heat-graphene" mode, the energy is flowing from the heated graphene to the cooled heneicosane). The effect of orientation of the perfect crystal structure (heneicosane molecules are positioned perpendicular and parallel to the graphene basal plane) on the interfacial thermal conductance has been examined. It is observed that the interfacial thermal conductance is 2 orders of magnitude higher under the heat-matrix mode than under the heat-graphene mode, for liquid or solid heneicosane and monolayer graphene. With an increase in the number of graphene layers, the interfacial thermal conductance under the heat-matrix mode decreases and reaches a plateau when the number of the graphene layer is more than eight. This is caused by the decreasing contribution of direct heat transfer from the matrix to matrix across the graphene layers via nonbonded intermolecular interactions. The interfacial thermal conductance becomes similar for both heating modes, once the number of graphene layers in the system is over 15. The influence of temperature on the interfacial thermal conductance is found to be insignificant in the range (175−250 K; 350−400 K). Both the phase and structure of heneicosane significantly influence the interfacial conductance. Spectral analysis suggests that graphene vibrational modes of all frequencies contribute to the interfacial heat transfer.

In order to study the phenomena where interfaces play a dominant role through molecular simulations, the proper representation of the interfacial thermodynamic properties of a given model is of crucial importance. The use of coarse-grained rather than atomistic models makes it possible to simulate interfacial systems with larger time and length scales. In the present work, we compare the structure and thermodynamic behavior of one atomistic and two single-site coarse-grained models of water on nonpolar surfaces, namely, graphite and the basal plane of molybdenum disulfide. The three models interact with the surfaces through Lennard-Jones potentials parametrized to reproduce recent experimental contact angle measurements. The models form a layered structure close to the surface, which is usually observed on sufficiently attractive nonpolar substrates. However, differences in the structure and thermodynamic behavior are observed between the models. These differences are explained by certain features of the water models, such as short range tetrahedral order and liquid density fluctuations. Besides these results, the approach employed in the present study may be used to assess the ability of coarse-grained models for solid-liquid systems to represent consistent interfacial thermodynamics.

Coarse-grained models have increasingly been used in large-scale particle-based simulations. However, due to their lack of degrees of freedom, it is a priori unlikely that they straightforwardly represent thermal properties with the same accuracy as their atomistic counterparts. We take a first step in addressing the impact of liquid coarse-graining on interfacial heat conduction by showing that an atomistic and a coarse-grained model of water may yield similar values of the Kapitza conductance on few-layer graphene with interactions ranging from hydrophobic to mildly hydrophilic. By design the water models employed yield similar liquid layer structures on the graphene surfaces. Moreover, they share common vibration properties close to the surfaces and thus couple with the vibrations of graphene in a similar way. These common properties explain why they yield similar Kapitza conductance values despite their bulk thermal conductivity differing by more than a factor of two.