(a) Modeled rates of fragmentation (solid green line), vibrational cooling (dotted red line) and recurrent fluorescence (dashed blue line). The region in between the horizontal dotted lines highlights the dynamical range covered experimentally. (b) TD-DFT-computed optical absorption spectrum of S₈⁺ (filled blue) and S₈ (red). The y-axis represents oscillator strength (f). A top axis in wavelength is included.