IQA analysis of the two-particle density matrix: chemical insight and computational efficiency

Abstract

The interacting quantum atoms (IQA) method offers a rigorous and minimal route to calculate atomic electron correlation energies from the two-particle density matrix (2PDM). The price paid is that this method is very time-consuming. However, employing CCSD and CCSD(T), we explore several approaches to speed up such calculations. We make the pivotal observation that the removal, from the true 2PDM, of both the Hartree–Fock part of the 2PDM and an approximate 2PDM (Müller) dramatically reduces the size of the quadrature grid needed to obtain accurate energies.