Benchmarking the accuracy of the separable resolution of the identity approach for correlated methods in the numeric atom-centered orbitals framework

Abstract

Four-center two-electron Coulomb integrals routinely appear in electronic structure algorithms. The resolution-of-the-identity (RI) is a popular technique to reduce the computational cost for the numerical evaluation of these integrals in localized basis-sets codes. Recently, Duchemin and Blase proposed a separable RI scheme [J. Chem. Phys. 150, 174120 (2019)], which preserves the accuracy of the standard global RI method with the Coulomb metric and permits the formulation of cubic-scaling random phase approximation (RPA) and GW approaches. Here, we present the implementation of a separable RI scheme within an all-electron numeric atom-centered orbital framework. We present comprehensive benchmark results using the Thiel and the GW100 test set. Our benchmarks include atomization energies from Hartree–Fock, second-order Møller–Plesset (MP2), coupled-cluster singles and doubles, RPA, and renormalized second-order perturbation theory, as well as quasiparticle energies from GW. We found that the separable RI approach reproduces RI-free HF calculations within 9 meV and MP2 calculations within 1 meV. We have confirmed that the separable RI error is independent of the system size by including disordered carbon clusters up to 116 atoms in our benchmarks.