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Fluorine and carbon K absorption and emission spectra of liquid perfluorodecalin are presented and analyzed in terms of density functional calculations-configuration interaction. A comprehensive view of the electronic structure is given, and site-specific intramolecular interactions are investigated in detail. It is found that, while the outer fluorine atoms have excess charge in the ground state, the lowest excitations must be associated with charge transfer towards the inner carbon atoms.

The electronic structure of perfluorodecalin studied by soft X-ray spectroscopy and electronic structure calculations