Rotationally resolved photoelectron spectrum of the methyl radical in the vicinity of the and photoionizing transitions. The black curve (panel a) is the experimental spectrum, the red one (panel b) the complete simulation and the blue and green ones (panels c and d) the separated simulations of the ionizing transitions to and , respectively. All simulations have been performed at 250 K and convolved with a Gaussian line shape (FWHM = 1.5 cm⁻¹).