PNNL

Abstract

We develop two multi-defect machine learning interatomic potentials (MLIPs) trained at the BLYP-D2 and PBE-D3 density functional theories using the DeepMD-kit, allowing for the investigation of structural and thermodynamic properties of nitric acid over a wide range of concentrations via molecular dynamics (MD) simulations. We directly compute the degree of dissociation, a, and pKa from MD simulations, revealing that HNO3 behaves as a weaker acid at higher concentrations, noting that our standard-state pKa value is in excellent agreement with the experimental one. In general, good agreement is observed with experimental results such as a and density outside the training dataset, with only modest deviations at low-to-medium concentrations. We benchmark our custom multi-defect DeepMD MLIPs against foundational models MACE-MP0 and MACE-OFF23. The foundation models capture some aspects of HNO3/No3- solvation in concentrated nitric acid but show noticeable density errors and miss subtle structural features relevant to spectroscopy, whereas the bespoke DeepMD MLIPs yield more compact solvation shells, reproduce density-concentration trends, and run ~12–15× faster than MACE-MP0. Although classical FFs are still more efficient and match experimental densities better, they lack chemical reactivity and thus cannot predict a or pKa, underscoring the need for system-specific reactive MLIPs beyond universal MLIPs.