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

TL;DR

This paper introduces tensor hypercontraction to improve the efficiency of fully self-consistent Green's function methods, enabling large-scale calculations and providing insights into their accuracy and physical behavior in intermolecular interactions.

Contribution

The authors develop an efficient THC-based algorithm for self-consistent Green's function methods, allowing large-scale calculations and analysis of the role of exchange diagrams in intermolecular interactions.

Findings

scGW slightly overbinds large systems, unlike non-self-consistent RPA

scGWSOX slightly underbinds large systems, due to exchange corrections

All methods shown to be size-extensive

Abstract

We apply tensor hypercontraction (THC) to reduce the computational scaling of expensive fully self-consistent Green's function methods. We present an efficient MPI-parallel algorithm and its implementation for evaluating the correlated second-order exchange term (SOX). This approach enabled us to conduct the largest fully self-consistent calculations with over 1100 atomic orbitals (AOs), with negligible errors attributed to THC fitting. Utilizing our THC implementation for scGW, scGF2, and scGWSOX (GW plus the SOX term iterated to achieve full Green's function self-consistency), 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.