Derivative Discontinuity in Many-Body Perturbation Theory and Chemical Potentials in Random Phase Approximation

We derive analytical expressions for chemical potentials within the random phase approximation (RPA), equivalently the $GW$ energy functional evaluated using non interacting Green's functions ($G_s$). The chemical potential is obtained using two formally equivalent approaches: a direct derivative of the total energy with respect to particle number, and a functional derivative via the chain rule through $G_s$, both validated with finite difference benchmarks. We show that the functional derivative of the $GW$ correlation energy$\unicode{x2013}$i.e., the $GW$ correlation self energy$\unicode{x2013}$exhibits a discontinuity at integer particle numbers with finite jumps. This resolves the apparent inconsistency between accurate $GW$ quasiparticle energies and the large delocalization errors observed in RPA total energies, as standard $GW$ self energies neglect this nonanalytic behavior. Our results suggest that derivative discontinuities are a fundamental feature of correlation energy functionals, analogous to the known discontinuity in the exact exchange correlation energy.