Electronic excitation energies of molecular systems from the Bethe-Salpeter equation: Example of the H2 molecule

Abstract: We review the Bethe-Salpeter equation (BSE) approach to the calculation of electronic excitation energies of molecular systems. We recall the general Green's function many-theory formalism and give the working equations of the BSE approach within the static GW approximation with and without spin adaptation in an orbital basis. We apply the method to the pedagogical example of the H2 molecule in a minimal basis, testing the effects of the choice of the starting one-particle Green's function. Using the non-interacting one-particle Green's function leads to incorrect energy curves for the first singlet and triplet excited states in the dissociation limit. Starting from the exact one-particle Green's function leads to a qualitatively correct energy curve for the first singlet excited state, but still an incorrect energy curve for the triplet excited state. Using the exact one-particle Green's function in the BSE approach within the static GW approximation also leads to a number of additional excitations, all of them being spurious except for one which can be identified as a double excitation corresponding to the second singlet excited state.