Coherent motion of excited state cyclic ketones: The have and the have-nots

The internal conversion processes of four cyclic ketones; cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone and cyclohexanone are investigated by Velocity Map Imaging (VMI) photoelectron spectroscopy. A 201 nm pump accesses the second excited state (n,3s) and the ultrafast dynamics is mapped by subsequent ionization with a 350 nm probe. Three of the four investigated molecular systems show an oscillatory time-dependence in the peak position of the 3s photoelectron band, while the last one simply decays exponentially. We find that the most plausible reason for the absence of the oscillation is due to high structural similarity between the excited state and the ionic state along the active coordinate.