Abstract
Taking the real chemical environment explicitly into account, a study of highly excited atom states carrying multiple vacancies revealed a nearly alchemical transmutation of the valence electron structure occurring prior to X-ray emission. While in third-row atoms such as Si an interatomic valence charge flow via covalent bonds was found to prevail in this electron rearrangement, the present study of F emitter atoms discloses the decisive role of adiabatic character-exchanging pseudo-crossings between descending levels of the emitter atom (F,2s,2p,3s,3p,3d) and the upper levels of adjacent atoms. These pseudo crossings, achieved by a temporary covalency, provide a concise and comprehensive picture of the chemical effects observed in the F K X-ray satellite and hypersatellite spectra. These chemical effects furnish evidence of creation and decay of inner-shell vacancies as a single scattering process in which electron relaxation efficiently competes with the sequential ejection of electrons.