Breaking the Coupled Cluster Barrier for Machine-Learned Potentials of Large Molecules: The Case of 15-Atom...

Machine-learned potential energy surfaces (PESs) for molecules with more than 10 atoms are typically forced to use lower-level electronic structure methods such as density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2). While these are efficient and realistic, they fall short of the accuracy of the "gold standard" coupled-cluster method, especially with respect to reaction and isomerization barriers. We report a major step forward in applying a Δ-machine learning method to the challenging case of acetylacetone, whose MP2 barrier height for H-atom transfer is low by roughly 1.1 kcal/mol relative to the benchmark CCSD(T) barrier of 3.2 kcal/mol. From a database of 2151 local CCSD(T) energies and training with as few as 430 energies, we obtain a new PES with a barrier of 3.5 kcal/mol in agreement with the LCCSD(T) barrier of 3.5 kcal/mol and close to the benchmark value. Tunneling splittings due to H-atom transfer are calculated using this new PES, providing improved estimates over previous ones obtained using an MP2-based PES.