How Good Is DFT for Solid-Liquid Interfaces? A Comparison With the Random-Phase Approximation for Water on Graphene
Year: 2026
Type: preprint
Abstract: Simulations of water at solid interfaces routinely disagree on basic properties, from contact angle to friction, depending on the model used, whether an empirical force field or a density functional theory (DFT) exchange-correlation (XC) approximation. Yet no accurate computational reference has been available to determine which, if any, is reliable. Here we assess XC approximations spanning the rungs of Jacob's Ladder against the random-phase approximation (RPA) at the graphene-water interface. Using machine-learned potentials (MLPs) trained on both DFT and RPA data, we achieve the extensive sampling required to characterize interfacial structure, wettability, friction, and vibrational sum-frequency generation spectra. We find that XC approximations disagree substantially with RPA and with each other. To make sense of this, we introduce a transferable, multi-observable scoring framework that distills each functional's agreement with RPA into a single measure. Six functionals emerge as reliable starting points for studies of graphene-water and other dispersion-dominated interfaces, namely B3LYP-D3(0), revPBE-D3(0), revPBE-D3(BJ), B97M-rV, r$^{2}$SCAN, and revPBE0-D3(0). Notably, this ranking follows no simple rule based on functional family or rung of Jacob's Ladder. What does hold across functionals is that dynamical and spectroscopic properties tend to be harder for DFT to reproduce than structural ones, with direct consequences for functional selection. Our framework also offers a general strategy for benchmarking any atomistic model, including the new generation of foundational MLPs, against high-accuracy references at solid--liquid interfaces. Beyond simulation, this work identifies which models can be trusted to connect measured contact angles, friction, and vibrational spectra to the molecular structure behind them.
Source: arXiv (Cornell University)
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: green
Awards: G1584869537, G169191358, Theoretical Condensed Matter Cambridge - Critical Mass Grant, G296868690, EPSRC Core Equipment Award 2022/23, G4392794930, G5275711260, G581313191, G6589181013, Cambridge Service for Data Driven Discovery (CSD3) - A National Data Intensive Science Cloud for Converged Simulation, AI & Analytics, G8116984139, G8727945938, G9001172685
OpenAlex ID: W7220909703