Fig. 2: X-ray K-edge absorption spectra of Mn₃.

a The experimental (red) and calculated (blue) ground state K-edge XAS of Mn₃. b XAS difference spectra at 700 fs after 400 nm photoexcitation. The calculated spectrum was simulated using the 74% excitation yield and calculating the XAS predominantly along ν60 to give the best match to the experimental results. Further details concerning the computations can be found in the methods section. c Time evolution of the TR-XAS signal at an X-ray probe energy of 6548.5 eV. The fitted line is made up of two exponential decay components with time constants τ₁ = 178 ± 6 fs and τ₂ = 9000 fs. There is also a small oscillatory component with a frequency of 172 ± 8 cm^–1 that is a signature of vibrational coherence. The data have been smoothed with a five-point adjacent average (the effect of smoothing is shown in Supplementary Fig. 2). The signal is normalised with respect to the ground state (laser off) signal. d Schematic of the mode (ν60) that is responsible for to oscillation seen in c, where the peripheral ligands of the Mn₃ complex have been removed for clarity. Mn, purple; O, red; N, blue. A video of this mode is provided in Supplementary Movie 1. Source data are provided in the Source Data folder.