Reactive Chemistry at the Unrestricted Coupled Cluster Level: High-Throughput Calculations for Training Machine Learning Potentials

Abstract

Modeling chemical reactions accurately at the atomistic level requires high-level electronic structure theory due to the presence of unpaired electrons and the need to properly describe the energetics of bond breaking and bond formation. Commonly used approaches such as density functional theory (DFT) frequently fail for this task due to deficiencies that are well recognized. However, for high-fidelity approaches, creating large data sets of energies and forces for reactive processes to train machine learning interatomic potentials (MLIPs) or force fields is daunting. For example, the use of the unrestricted coupled cluster level of theory has previously been seen as unfeasible due to high computational costs, the lack of analytical gradients in many computational codes, and additional challenges such as constructing suitable basis set corrections for forces. In this work, we develop new methods and workflows to overcome the challenges inherent to automating unrestricted coupled cluster calculations. Using these advancements, we create a data set of gas-phase reactions containing energies and forces for 3119 different organic molecules configurations calculated at the gold-standard level of unrestricted CCSD(T) (coupled cluster singles doubles and perturbative triples). With this data set, we provide an analysis of the differences between the density functional and unrestricted CCSD(T) descriptions. We develop a transferable MLIP for gas-phase reactions, trained on unrestricted CCSD(T) data, and demonstrate the advantages of transitioning away from DFT data. Transitioning from training to DFT to training to UCCSD(T) data sets yields an improvement of more than 0.1 eV/Å in force accuracy and over 0.1 eV in activation energy reproduction.