We present an ab initio approach for computing the photoionization spectrum near autoionization resonances in multi-electron systems. While traditional (Hermitian) theories typically require computing the continuum states, which are difficult to obtain with high accuracy, our non-Hermitian approach requires only discrete bound and metastable states, which can be accurately computed with available quantum chemistry tools. We derive a simple formula for the absorption line shape near Fano resonances, which relates the asymmetry of the spectral peaks to the phase of the complex transition dipole moment. Additionally, we present a formula for the ionization spectrum of laser-driven targets and relate the "Autler-Townes" splitting of spectral lines to the existence of exceptional points in the Hamiltonian. We apply our formulas to compute the autoionization spectrum of helium, but our theory is also applicable for nontrivial multi-electron atoms and molecules.
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