Low-Data Deep Quantum Chemical Learning for Accurate MP2 and Coupled-Cluster Correlations

Abstract

<p> Accurate ab initio prediction of electronic energies is very expensive for macromolecules by explicitly solving post-Hartree-Fock equations. We here exploit the physically justified local correlation feature in a compact basis of small molecules and construct an expressive low-data deep neural network (dNN) model to obtain machine-learned electron correlation energies on par with MP2 and CCSD levels of theory for more complex molecules and different datasets that are not represented in the training set. We show that our dNN-powered model is data efficient and makes highly transferable predictions across alkanes of various lengths, organic molecules with non-covalent and biomolecular interactions, as well as water clusters of different sizes and morphologies. In particular, by training 800 (H₂O)₈ clusters with the local correlation descriptors, accurate MP2/cc-pVTZ correlation energies up to (H₂O)₁₂₈ can be predicted with a small random error within chemical accuracy from exact values, while a majority of prediction deviations are attributed to an intrinsically systematic error. Our results reveal that an extremely compact local correlation feature set, which is poor for any direct post-Hartree-Fock calculations, has however a prominent advantage in reserving important electron correlation patterns for making accurate transferable predictions across distinct molecular compositions, bond types, and geometries. <br></p>