Fig. 3: Valence-to-core x-ray emission.
a The upper inset shows difference spectra in the valence-to-core (VtC) region for different time bins. Shaded areas reflect the standard deviation within a time bin when all difference spectra are rescaled to the bin-averaged summed difference signal magnitude. The black line (LMCT model) represents the difference between the ground state spectra of the aqueous 1[FeII(CN)6]4- and 2[FeIII(CN)6]3− complexes. The lower inset shows the experimental 2[FeIII(CN)6]3− ground state spectrum (black) with the calculated transitions (blue). b Time dependence of the first moment position \({\Delta \mu }_{1,{VtC}}\) (red) with a kinetic fit (black). The estimation of uncertainties is described in Supplementary Note 4. c Time dependence of the VtC intensity change \(\Delta {I}_{{VtC}}\) (red) with a kinetic fit (black). The estimation of uncertainties is described in Supplementary Note 4. d Comparison between the 1.5–3 ps difference spectrum and calculated difference spectra for various candidate species as described in the text. Scaling factors of the calculated differences result from fitting the experimental difference in the 1.5–3 ps range and directly represent population fractions. Vertical dashed lines at 7104.23 eV, 7105.64 eV, 7109.43 eV, and 7111.84 eV are shown to facilitate comparisons between difference spectra.
