Many-body GW calculations with very large scale polarizable environments made affordable: A fully ab initio QM/QM approach

Abstract

We present a many-body GW formalism for quantum subsystems embedded in discrete polarizable environments containing up to several hundred thousand atoms described at a fully ab initio random phase approximation level. Our approach is based on a fragment approximation in the construction of the Green’s function and independent-electron susceptibilities. Further, the environing fragments susceptibility matrices are reduced to a minimal but accurate representation preserving low order polarizability tensors through a constrained minimization scheme. This approach dramatically reduces the cost associated with inverting the Dyson equation for the screened Coulomb potential W, while preserving the description of short to long-range screening effects. The efficiency and accuracy of the present scheme is exemplified in the paradigmatic cases of fullerene bulk, surface, subsurface, and slabs with varying number of layers.