High resolution F1s absorption spectra of solid fluorides of 3d elements

The near-edge fine structure of the 1s absorption spectrum of fluorine atoms from solid-state fluorides of some elements belonging to the first-row transition series was studied for the first time with a high-energy resolution. The spectra were measured with the method of total electron yield by using the Russian-German beamline of monochromatized synchrotron radiation at the electron storage ring BESSY II. The fine structure in the spectra of these most ionic compounds of the 3d atoms is analyzed from comparison of their spectra with the absorption spectrum of fluorine in TiF ₆ ^2? molecular anions from the K₂TiF₆ crystal. The latter absorption spectrum is preliminarily identified by its simultaneous consideration with the 2p absorption spectrum of titanium in TiF ₆ ^2? and the spectrum of fluorine in PF ₆ ^? anions from the KPF₆ crystal and in free SF₆ molecules. The lowest free electronic states are shown to form due to covalent mixing of the 3d states of a metal atom with the 2p states of the nearest fluorine atoms.