Energy-specific Bethe–Salpeter equation implementation for efficient optical spectrum calculations

Abstract

We present an energy-specific Bethe–Salpeter equation (BSE) implementation for efficient core and valence optical spectrum calculations. In the energy-specific BSE, high-lying excitation energies are obtained by constructing trial vectors and expanding the subspace targeting excitation energies above the predefined energy threshold in the Davidson algorithm. To calculate optical spectra over a wide energy range, energy-specific BSE can be applied to multiple consecutive small energy windows, where trial vectors for each subsequent energy window are made orthogonal to the subspace of preceding windows to accelerate the convergence of the Davidson algorithm. For seven small molecules, energy-specific BSE combined with G0W0 provides small errors around 0.8 eV for absolute and relative K-edge excitation energies when starting from a hybrid PBEh solution with 45% exact exchange. We further showcase the computational efficiency of this approach by simulating the N 1s K-edge excitation spectrum of the porphine molecule and the valence optical spectrum of silicon nanoclusters involving 6000 excited states using G0W0-BSE. This work expands the applicability of the GW-BSE formalism for investigating high-energy excited states of large systems.