Fully Dynamic 32 Self-Energy for Finite Systems: Formulas and Benchmark.

Over the years, Hedin's self-energy has been proven to be a rather accurate and simple approximation to evaluate electronic quasiparticle energies in solids and in molecules. Attempts to improve over the simple approximation, the so-called vertex corrections, have been constantly proposed in the literature. Here, we derive, analyze, and benchmark the complete second-order term in the screened Coulomb interaction for finite systems. This self-energy named 32 contains all the possible time orderings that combine 3 Green's functions and 2 dynamic . We present the analytic formula and its imaginary frequency counterpart, with the latter allowing us to treat larger molecules. The accuracy of the 32 self-energy is evaluated on well-established benchmarks (GW100, Acceptor 24, and Core 65) for valence and core quasiparticle energies. Its link with the simpler static approximation, named SOSEX for static screened second-order exchange, is analyzed, which leads us to propose a more consistent approximation named 2SOSEX. In the end, we find that neither the 32 self-energy nor any of the investigated approximations to it improve over one-shot with a good starting point. Only quasi-particle self-consistent HOMO energies are slightly improved by addition of the 32 self-energy correction. We show that this is due to the self-consistent update of the screened Coulomb interaction, leading to an overall sign change of the vertex correction to the frontier quasiparticle energies.