Extrapolation to the Limit of a Complete Pair Natural Orbital Space in Local Coupled-Cluster Calculations

Abstract

The domain-based local pair natural orbital (PNO) coupled-cluster DLPNO-CCSD(T) method allows one to perform single point energy calculations for systems with hundreds of atoms while retaining essentially the accuracy of its canonical counterpart, with errors that are typically smaller than 1 kcal/mol for relative energies. Crucial to the accuracy and efficiency of the method is a proper definition of the virtual space in which the coupled-cluster equations are solved, which is spanned by a highly compact set of pair natural orbitals (PNOs) that are specific for each electron pair. The dimension of the PNO space is controlled by the T _CutPNO threshold: only PNOs with an occupation number greater than T _CutPNO are included in the correlation space of a given electron pair, whilst the remaining PNOs are discarded. To keep the error of the method small, a conservative T _CutPNO value is used in standard DLPNO-CCSD(T) calculations. This often leads to unnecessarily large PNO spaces, which limits the efficiency of the method. Herein, we introduce a new computational strategy to approach the complete PNO space limit (for a given basis set) that consists in extrapolating the results obtained with different T _CutPNO values. The method is validated on the GMTKN55 set using canonical CCSD(T) data as the reference. Our results demonstrate that a simple two-point extrapolation scheme can be used to significantly increase the efficiency and accuracy of DLPNO-CCSD(T) calculations, thus extending the range of applicability of the technique.