Data-Driven Many-Body Potentials from Density Functional Theory for Aqueous Phase Chemistry

02 January 2023, Version 2
This content is a preprint and has not undergone peer review at the time of posting.


Density functional theory (DFT) has been applied to modeling molecular interactions in water for over three decades. The ubiquity of water in chemical and biological processes demands a unified understanding of its physics, from the single-molecule to the thermodynamic limit and everything in between. Recent advances in the development of data-driven and machine-learning potentials have accelerated simulation of water and aqueous systems with DFT accuracy. However, the anomalous properties of water in the condensed phase, where a rigorous treatment of both local and non-local many-body interactions is in order, is often unsatisfactory or partially missing in DFT models of water. In this review, we discuss the modeling of water and aqueous systems based on DFT, and provide a comprehensive description of a general theoretical/computational framework for the development of data-driven many-body potentials from DFT reference data. This framework, coined MB-DFT, readily enables efficient many-body molecular dynamics (MB-MD) simulations of small molecules, in both gas and condensed phases, while preserving the accuracy of the underly- ing DFT model. Theoretical considerations are emphasized, including the role that the delocalization error plays in MB-DFT potentials of water, and the possibility to elevate DFT and MB-DFT to near-chemical-accuracy through a density-corrected formalism. The development of the MB-DFT framework is described in detail, along with its application in MB-MD simulations and recent extension to the modeling of reactive processes in solution within a quantum mechanics/many-body molecular mechanics (QM/MB-MM) scheme, using water as a prototypical solvent. Finally, we identify open challenges and discuss future directions for MB-DFT and QM/MB-MM simulations in condensed phases.


density functional theory
molecular dynamics
delocalization error
density-corrected DFT
supercooled water
quantum mechanics/molecular mechanics
machine learning
data-driven models
many-body interactions


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