Photoelectric absorption is characterized by a smooth power-law decrease of the cross section with photon energy. Absorption edges reveal rich structure, which continues into the high-energy side. The quasiperiodic signal, superposed onto the smooth basis, due to scattering of the photoelectron on the neighbours of the target atom provides the basis for the structural (XAFS) analysis of the material. Irregular tiny resonances and edges that appear over the same general range as XAFS are recognized as intra-atomic effects: multielectron excitations (MEE) owing to correlated motion in the electronic cloud. The systematic study of MEE began on noble gases and metallic vapours, both of which are gases of free atoms. With some extremely strong MEE, mostly coexcitations of the sub­valence d and f electrons, the structural XAFS analysis may be compromised; hence, there is a need to independently determine the MEE signal, the atomic absorption background (AAB) for the analyzed element, and remove it prior to analysis. In view of the scarcity of elements which can practically be prepared in a free-atom gas state, several approaches to approximate the AAB have been developed: analysis of disordered compounds, where the weak and simple XAFS signal can be modelled and removed, and correlation analysis of the absorption spectra of several independent samples, where the AAB is extracted in an iterative procedure.