In:
Physical Chemistry Chemical Physics, Royal Society of Chemistry (RSC), Vol. 24, No. 33 ( 2022), p. 19890-19894
Abstract:
Oxidation states are integer in number but d n configurations of transition metal centers vary continuously in polar bonds. We quantify the shifts of the iron L 3 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] + .
Type of Medium:
Online Resource
ISSN:
1463-9076
,
1463-9084
Language:
English
Publisher:
Royal Society of Chemistry (RSC)
Publication Date:
2022
detail.hit.zdb_id:
1476283-3
detail.hit.zdb_id:
1476244-4
detail.hit.zdb_id:
1460656-2
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