Optical spectra of small silver clusters with the Bethe–Salpeter formalism: A reassessment

Abstract

We study the optical absorption spectra of small Agn (n = 2, 4, 6, 8) clusters using the Bethe–Salpeter equation (BSE) formalism with a Hamiltonian built from GW quasiparticle energies. Calculations are based on an effective core potential including the 4sp shells in the valence. Non-self-consistent G0W0 calculations relying on input Kohn–Sham eigenstates generated with semilocal functionals lead to very poor BSE absorption spectra, confirming a previous observation. However, eigenvalue or quasiparticle self-consistent GW calculations dramatically improve the agreement with experiments and TD-DFT spectra obtained with range-separated hybrid functionals. The importance of the position of the 4d occupied band is emphasized.