Influence of the photoionization process on the fragmentation of laser desorbed polycyclic aromatic hydrocarbons

Characterization of polycyclic aromatic hydrocarbons (PAHs) samples has been performed by laser desorption combined with multi-photon ionization technique using two different geometries of the ionization laser beam. This comparative study evidences the strong influence of ionization laser fluence on PAH fragmentation. Through a ∼103 enlargement of the ionization probe volume and 104 reduction of laser fluence over previous studies, fragment free mass spectra are obtained with higher sensitivity and selectivity. The ability to measure fragment free PAH mass spectra is a very important step in the end goal of measuring complex unknown mixtures of PAH desorbed from solid surface such as soot samples.