Neural network interaction potentials for para-hydrogen with flexible molecules

Abstract

The study of molecular impurities in para-hydrogen ( pH2) clusters is key to push forward our understanding of intra- and intermolecular interactions, including their impact on the superfluid response of this bosonic quantum solvent. This includes tagging with only one or very few pH2, the microsolvation regime for intermediate particle numbers, and matrix isolation with many solvent molecules. However, the fundamental coupling between the bosonic pH2 environment and the (ro-)vibrational motion of molecular impurities remains poorly understood. Quantum simulations can, in principle, provide the necessary atomistic insight, but they require very accurate descriptions of the involved interactions. Here, we present a data-driven approach for the generation of impurity⋯ pH2 interaction potentials based on machine learning techniques, which retain the full flexibility of the dopant species. We employ the well-established adiabatic hindered rotor (AHR) averaging technique to include the impact of the nuclear spin statistics on the symmetry-allowed rotational quantum numbers of pH2. Embedding this averaging procedure within the high-dimensional neural network potential (NNP) framework enables the generation of highly accurate AHR-averaged NNPs at coupled cluster accuracy, namely, explicitly correlated coupled cluster single, double, and scaled perturbative triples, CCSD(T*)-F12a/aVTZcp, in an automated manner. We apply this methodology to the water and protonated water molecules as representative cases for quasi-rigid and highly flexible molecules, respectively, and obtain AHR-averaged NNPs that reliably describe the corresponding H2O⋯ pH2 and H3O+⋯ pH2 interactions. Using path integral simulations, we show for the hydronium cation, H3O+, that umbrella-like tunneling inversion has a strong impact on the first and second pH2 microsolvation shells. The automated and data-driven nature of our protocol opens the door to the study of bosonic pH2 quantum solvation for a wide range of embedded impurities.