Koopmans Meets Bethe-Salpeter: Excitonic Optical Spectra without GW

Abstract

The Bethe-Salpeter equation (BSE) can be applied to compute from first-principles optical spectra that include the effects of screened electron-hole interactions. As input, BSE calculations require single-particle states, quasiparticle energy levels, and the screened Coulomb interaction, which are typically obtained with many-body perturbation theory, whose cost limits the scope of possible applications. This work tries to address this practical limitation, instead deriving spectral energies from Koopmans-compliant functionals and introducing a new methodology for handling the screened Coulomb interaction. The explicit calculation of the W matrix is bypassed via a direct minimization scheme applied on top of a maximally localized Wannier function basis. We validate and benchmark this approach by computing the low-lying excited states of the molecules in Thiel's set and the optical absorption spectrum of a C₆₀ fullerene. The results show the same trends as quantum chemical methods and are in excellent agreement with previous simulations carried out at the time-dependent density functional theory or G₀ W₀-BSE level. Conveniently, the new framework reduces the parameter space controlling the accuracy of the calculation, thereby simplifying the simulation of charge-neutral excitations, offering the potential to expand the applicability of first-principles spectroscopies to larger systems of applied interest.