Fig. 3: Dissociation of CO ligands and the resulting Fe(CO)4 dynamics across multiple pair distances. | Nature Communications

Fig. 3: Dissociation of CO ligands and the resulting Fe(CO)4 dynamics across multiple pair distances.

From: Real-space observation of the dissociation of a transition metal complex and its concurrent energy redistribution

Fig. 3

a Within the range 1.3 < R < 2.3 Å, steady-state Fe-C pair density tracks CO losses and ground-state Fe-C motions. A kinetic model (dashed yellow) fitted to the measured  − ΔPD averaged in this range (blue), and compared to simulated pair-density dynamics (red), which only account for the first CO loss. The model yields rates of 101 ± 13 fs (dotted black) and 3 ± 0.5 ps (green) for the first and second dissociation, respectively (see text). b Predissociation oscillations are observed at 3.7 < R < 7 Å, with the first CO loss marked by a strong peak around 250 fs as Fe-C and Fe-O pairs traverse this distance range. c For R > 7 Å, the first CO loss occurs after 450 fs, followed by the second CO loss visible after 1 ps. d Fourier analysis of δ(τ), the residual between the fitted CO1+CO2 and measured PD in α (inset) reveals a peak at 78 ± 16 cm−1, attributed to C-Fe-C bending modes in hot Fe(CO)4, as determined by normal mode analysis fit (Supplementary Note 7). e Wavelet analysis of δ(τ) shows the delayed onset of the 78 cm−1 component relative to the prompt 266 cm−1 due to predissociation oscillations.

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