High Accuracy Many-Body Calculational Approaches for Excitations in Molecules

Abstract

Two state-of-the-art computational approaches: quantum Monte Carlo (QMC), based on accurate total energies, and GW with exciton effects (GW-BSE), based on perturbation theory are employed to calculate ionization potentials, electron affinities, and first excited singlet and triplet energies for the silane and methane molecules. Results are in excellent agreement between these dramatically different approaches and with available experiment. The optically forbidden triplet excitation in silane is predicted to lie roughly 1 eV higher than previously reported. For methane, the impact of geometry relaxation is shown to be \(\sim\) 2 eV for excited states. Further, in the GW-BSE method, we demonstrate that inclusion of off-diagonal matrix elements in the self-energy operator is crucial for an accurate picture.