Registry-Dependent Potential for Interfaces of Water with Graphene

Abstract

An anisotropic interlayer potential that can accurately describe the van der Waals interaction of the water− graphene interface is presented. The force field is benchmarked against the many-body dispersion-corrected density functional theory. The parametrization of the interlayer potential demonstrates a satisfactory agreement with the reference data set of binding energy curves and sliding potential energy surfaces for various configurations of a water molecule deposited on monolayer graphene, indicating that the developed force field significantly enhances the accuracy in the empirical description of water− graphene interfacial interactions. The water contact angles of monolayer and multilayer graphene extracted from molecular dynamics simulations based on this force field are close to the experimental measurements and predict the hydrophilic nature of graphene. The theoretical approach proposed in this work can be easily adapted to heterointerfaces formed with water and other two-dimensional materials, providing a reliable and versatile platform for studying the wetting properties of these materials.

Anisotropic Interfacial Force Field for Interfaces of Water with Hexagonal Boron Nitride

“…First, we calculated the WCA of a water droplet deposited on a monolayer pristine h -BN substrate using the radial density profile method (Figure a). This approach has been previously validated and demonstrated to yield reliable results, particularly when applied in conjunction with the TIP4P/2005 water model as employed in our previous study . In MD simulations, periodic boundary conditions were applied for the lateral directions of the h -BN substrate, and a simulation box with dimensions of 19.816 × 201.455 × 15.000 nm was employed to ensure the exclusion of self-interactions between water molecule images.…”

“…Further MD simulation setup and computational details of the FEP method can be found in Section S5, from which we obtained W SL = 95.7 mJ/m 2 . Following the same protocol presented in ref , the surface tension of the water on h -BN, γ lv , is calculated as 66.5 mJ/m 2 . Substituting W SL and γ lv into eq , the WCA of the roughened h -BN surface with atomic step edges was calculated as θ = 64.0°, which exhibits good agreement with experimental measurements. , Notably, we find that the average values of the receding contact (49°) and the advancing contact (71°) obtained from the density profile method are in close agreement with the contact angle obtained from the FEP method.…”

“…In this study, we demonstrate that the AIP achieves excellent agreement with all of the DFT reference data sets, highlighting its capability to accurately describe the vdW interaction between water and h -BN heterointerfaces. In contrast, the LJ potential fails to capture the anisotropic characteristics of the vdW interaction in these systems, as it cannot adequately parametrize two BE curves with a single set of parameters, let alone capture the behavior of sliding PESs. , These results highlight the superiority of our AIP in providing a more self-consistent and reliable description of the vdW interaction between water molecules and h -BN compared with the LJ potential. When utilizing the AIP, we obtained a calculated WCA of approximately 115° for atomically flat pristine h -BN, indicating its hydrophobic nature.…”

“…Inspired by the successful application of the registry-dependent interlayer potential to 2D layered materials, − we developed anisotropic interfacial potential (AIP) to accurately describe the interaction between water molecules and h -BN in the current work. Note that the anisotropic interlayer force field for describing the vdW interaction between h -BN layers has already been established. , In our previous work investigating the water/graphene heterointerface, we demonstrated that the accuracy of the developed AIP strongly depends on the accuracy of the DFT reference data used for parameterization. In recent studies by Al-Hamdani et al, the performance of various DFT exchange-correlation functionals, including CCSD­(T), LRDMC, DMC, MP2, and RPA methods, , was investigated in terms of their ability to accurately predict the binding energy (BE) of water molecules on the h -BN surface.…”

“…Here, BE curves and sliding potential energy surfaces (PESs) for various H 2 O/ h -BN configurations were calculated to capture the anisotropic nature of the vdW interaction between the water molecule and h -BN. The importance of sliding PESs for accurately investigating the vdW interaction between water and 2D materials, which was overlooked in most previous theoretical studies, has been pointed out in recent studies. , The inclusion of sliding PESs in force field development is crucial for accurately investigating the transport and tribological characteristics of water on 2D materials …”