How Good Is DFT for Solid-Liquid Interfaces? A Comparison With the Random-Phase Approximation for Water on Graphene
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, r2SCAN, 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.
Related
- Hydrophilicity as Compensation of Hydrogen-Bond Defects at Graphene Oxide Interfaces.
- Engineering graphene oxide interfaces for electrochemical biosensing of biomolecules, cells, and organoids
- Mechano-electrochemical energy harvesting and self-powered sensing via dynamic liquid metal–electrolyte interfaces
- Systematic Investigation of Classical Molecular Dynamics Models for Ionic Liquid‐Based Electrolytes at Electrode Interfaces
- A Reductionist Molecular Dynamics Framework for Identifying Molecular Descriptors of Hydration at Solid–Liquid Biomaterial Interfaces
BibTeX
@misc{advincula2026good,
title = {{How Good Is DFT for Solid-Liquid Interfaces? A Comparison With the Random-Phase Approximation for Water on Graphene}},
author = {Xavier R. Advincula and Yair Litman and Jiuyang Shi and Flaviano Della Pia and Christoph Schran and Angelos Michaelides},
howpublished = {arXiv},
year = {2026},
month = oct,
doi = {10.48550/arxiv.2610.09685},
eprint = {2610.09685},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2610.09685},
note = {CC BY 4.0},
}
RIS
TY - UNPB
TI - How Good Is DFT for Solid-Liquid Interfaces? A Comparison With the Random-Phase Approximation for Water on Graphene
AU - Xavier R. Advincula
AU - Yair Litman
AU - Jiuyang Shi
AU - Flaviano Della Pia
AU - Christoph Schran
AU - Angelos Michaelides
PY - 2026
DA - 2026/10/07
PB - arXiv
DO - 10.48550/arxiv.2610.09685
UR - https://arxiv.org/abs/2610.09685
AB - 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^2SCAN, 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.
ER -