Exploration of the Two-Electron Excitation Space with Data-Driven Coupled Cluster

Abstract

Computational cost limits the applicability of post-Hartree-Fock methods such as coupled-cluster on larger molecular systems. The data-driven coupled-cluster (DDCC) method applies machine learning to predict the coupled-cluster two-electron amplitudes (t₂) using data from second-order perturbation theory (MP2). One major limitation of the DDCC models is the size of training sets that increases exponentially with the system size. Effective sampling of the amplitude space can resolve this issue. Five different amplitude selection techniques that reduce the amount of data used for training were evaluated, an approach that also prevents model overfitting and increases the portability of data-driven coupled-cluster singles and doubles to more complex molecules or larger basis sets. In combination with a localized orbital formalism to predict the CCSD t₂ amplitudes, we have achieved a 10-fold error reduction for energy calculations.