States with core- or inner-shell vacancies, which are commonly created by absorption of high-energy photons, can decay by a two-electron process in which one electron fills the core hole and the second one is ejected. These processes accompany many X-ray spectroscopies. Depending on the nature of the initial core- or inner-shell-hole state and the decay valence-hole state, these processes are called Auger decay, intermolecular Coulomb decay, or electron-transfer-mediated decay. To connect many-body wave functions of the initial and final states with the molecular orbital picture of the decay, we introduce the concept of natural Auger orbitals (NAOs). NAOs are obtained by a two-step singular value decomposition of the two-body Dyson orbitals, reduced quantities that enter the expression of the decay rate in the Feshbach-Fano treatment. NAOs afford chemical insight and interpretation of the high-level ab initio calculations of Auger decay and related two-electron relaxation processes.
