Delta-learned force fields for nonbonded interactions: Addressing the strength mismatch between covalent-nonbonded interaction for global models

TL;DR

This paper introduces -sGDML, a scale-aware machine learning approach that improves the accuracy of noncovalent force fields by decoupling intra- and intermolecular interactions, leading to more reliable molecular simulations.

Contribution

The paper presents -sGDML, a novel fragment-specific training method that enhances noncovalent force field accuracy in global models by addressing force label and descriptor mismatches.

Findings

-sGDML reduces fragment-resolved force errors by up to 75%.

The method maintains energy accuracy comparable to single global models.

Molecular dynamics simulations show improved stability across temperature ranges.

Abstract

Noncovalent interactions--vdW dispersion, hydrogen/halogen bonding, ion-$\pi$, and $\pi$-stacking--govern structure, dynamics, and emergent phenomena in materials and molecular systems, yet accurately learning them alongside covalent forces remains a core challenge for machine-learned force fields (MLFFs). This challenge is acute for global models that use Coulomb-matrix (CM) descriptors compared under Euclidean/Frobenius metrics in multifragment settings. We show that the mismatch between predominantly covalent force labels and the CM's overrepresentation of intermolecular features biases single-model training and degrades force-field fidelity. To address this, we introduce \textit{$\Delta$-sGDML}, a scale-aware formulation within the sGDML framework that explicitly decouples intra- and intermolecular physics by training fragment-specific models alongside a dedicated binding model, then composing them at inference. Across benzene dimers, host-guest complexes (C$_{60}$@buckycatcher, NO$_3^-$@i-corona[6]arene), benzene-water, and benzene-Na$^+$, \mbox{$\Delta$-sGDML} delivers consistent gains over a single global model, with fragment-resolved force-error reductions up to \textbf{75\%}, without loss of energy accuracy. Furthermore, molecular-dynamics simulations further confirm that the $\Delta$-model yields a reliable force field for C$_{60}$@buckycatcher, producing stable trajectories across a wide range of temperatures (10-400~K), unlike the single global model, which loses stability above $\sim$200~K. The method offers a practical route to homogenize per-fragment errors and recover reliable noncovalent physics in global MLFFs.