Assessing Permutationally Invariant Polynomial and Symmetric Gradient Domain Machine Learning Potential Energy Surfaces for H3O2–

The singly hydrated hydroxide anion OH-(H2O) is of central importance to a detailed molecular understanding of water; therefore, there is strong motivation to develop a highly accurate potential to describe this anion. While this is a small molecule, it is necessary to have an extensive data set of energies and, if possible, forces to span several important stationary points. Here, we assess two machine-learned potentials, one using the symmetric gradient domain machine learning (sGDML) method and one based on permutationally invariant polynomials (PIPs). These are successors to a PIP potential energy surface (PES) reported in 2004. We describe the details of both fitting methods and then compare the two PESs with respect to precision, properties, and speed of evaluation. While the precision of the potentials is similar, the PIP PES is much faster to evaluate for energies and energies plus gradient than the sGDML one. Diffusion Monte Carlo calculations of the ground vibrational state, using both potentials, produce similar large anharmonic downshift of the zero-point energy compared to the harmonic approximation of the PIP and sGDML potentials. The computational time for these calculations using the sGDML PES is roughly 300 times greater than using the PIP one.