Iron L3-edge energy shifts for the full range of possible 3d occupations within the same oxidation state of iron halides

Abstract

Oxidation states are integer in number but dⁿ configurations of transition metal centers vary continuously in polar bonds. We quantify the shifts of the iron L₃ excitation energy, within the same formal oxidation state, in a systematic L-edge X-ray absorption spectroscopy study of diatomic gas-phase iron(II) halide cations, [FeX]⁺,where X = F, Cl, Br, I. These shifts correlate with the electronegativity of the halogen, and are attributed exclusively to a fractional increase in population of 3d-derived orbitals along the series as supported by charge transfer multiplet simulations and density functional theory calculations. We extract an excitation energy shift of 420 meV ± 60 meV spanning the full range of possible 3d occupations between the most ionic bond in [FeF]⁺ and covalently bonded [FeI]⁺.