Towards Routine Condensed Phase Simulations with Delta-Learned Coupled Cluster Accuracy: Application to Liquid Water

High Resolution Image Download MS PowerPoint Slide Simulating liquid water to an accuracy that matches its wealth of available experimental data requires both precise electronic structure methods and reliable sampling of nuclear (quantum) motion. This is challenging because applying the electronic structure method of choice, coupled cluster theory with single, double, and perturbative triple excitations [CCSD(T)] to condensed phase systems, is currently limited by its computational cost and complexity. Recent tour de force efforts have demonstrated that this accuracy can indeed bring simulated liquid water into close agreement with experiment using machine learning potentials (MLPs). However, achieving this remains far from routine, requiring large datasets and significant computational cost. In this work, we introduce a practical approach that combines developments in MLPs with local correlation approximations to enable routine CCSD(T)-level simulations of liquid water. When combined with nuclear quantum effects, we achieve agreement with experiments for structural and transport properties. Importantly, the approach also handles constant-pressure simulations, enabling MLP-based CCSD(T) models to predict isothermal–isobaric bulk properties, such as water’s density maximum, in close agreement with experiment. Encompassing tests across electronic structure, datasets, and MLP architecture, this work provides a practical blueprint towards routinely developing CCSD(T)-based MLPs for the condensed phase.