Self-consistent GW via conservation of spectral moments

Abstract

We expand on a recently introduced alternate framework for $GW$ simulation of charged excitations [Scott et. al., J. Chem. Phys., 158, 124102 (2023)], based around the conservation of directly computed spectral moments of the GW self-energy. Featuring a number of desirable formal properties over other implementations, we also detail efficiency improvements and a parallelism strategy, resulting in an implementation with a demonstrable similar scaling to an established Hartree--Fock code, with only an order of magnitude increase in cost. We also detail the applicability of a range of self-consistent $GW$ variants within this framework, including a scheme for full self-consistency of all dynamical variables, whilst avoiding the Matsubara axis or analytic continuation, allowing formal convergence at zero temperature. By investigating a range of self-consistency protocols over the GW100 molecular test set, we find that a little-explored self-consistent variant based around a simpler coupled chemical potential and Fock matrix optimization to be the most accurate self-consistent $GW$ approach. Additionally, we validate recently observed evidence that Tamm--Dancoff based screening approximations within $GW$ lead to higher accuracy than traditional random phase approximation screening over these molecular test cases. Finally, we consider the Chlorophyll A molecule, finding agreement with experiment within the experimental uncertainty, and a description of the full-frequency spectrum of charged excitations.