Tensor hypercontraction for fully self-consistent imaginary-time GF2 and GWSOX methods: Theory, implementation, and role of the Green’s function second-order exchange for intermolecular interactions

Abstract

We present an efficient MPI-parallel algorithm and its implementation for evaluating the self-consistent correlated second-order exchange term (SOX), which is employed as a correction to the fully self-consistent GW scheme called scGWSOX (GW plus the SOX term iterated to achieve full Green’s function self-consistency). Due to the application of the tensor hypercontraction (THC) in our computational procedure, the scaling of the evaluation of scGWSOX is reduced from O(nτnAO5) to O(nτN2nAO2). This fully MPI-parallel and THC-adapted approach enabled us to conduct the largest fully self-consistent scGWSOX calculations with over 1100 atomic orbitals with only negligible errors attributed to THC fitting. Utilizing our THC implementation for scGW, scGF2, and scGWSOX, we evaluated energies of intermolecular interactions. This approach allowed us to circumvent issues related to reference dependence and ambiguity in energy evaluation, which are common challenges in non-self-consistent calculations. We demonstrate that scGW exhibits a slight overbinding tendency for large systems, contrary to the underbinding observed with non-self-consistent RPA. Conversely, scGWSOX exhibits a slight underbinding tendency for such systems. This behavior is both physical and systematic and is caused by exclusion-principle violating diagrams or corresponding corrections. Our analysis elucidates the role played by these different diagrams, which is crucial for the construction of rigorous, accurate, and systematic methods. Finally, we explicitly show that all perturbative fully self-consistent Green’s function methods are size-extensive and size-consistent.