Ionisation and fragmentation dynamics of laser desorbed polycyclic aromatic hydrocarbons using femtosecond and nanosecond post-ionisation

Nanosecond laser desorption/femtosecond laser mass spectrometry (LD/FLMS) incorporating a reflectron time-of-flight mass spectrometer has been used to study the ionisation/fragmentation of polycyclic aromatic hydrocarbons (PAHs) in intense laser fields (7.0×1014 to 9.3×1015 W cm−2). Pulses of 80 fs, 800 nm have been used to post-ionise the PAHs anthracene, tetracene and pentacene. For each molecule strong singly and doubly charged parent ions are observed accompanied by fragmentation. In addition, strong triply charged parent ions (M3+) are observed for anthracene and weaker M3+ signals for tetracene and pentacene are also observed. Nanosecond post-ionisation (266 nm, 16 ns) spectra of the molecules have been recorded and are included for comparison with the femtosecond data. Similarities in the observed fragmentation pattern of low-mass fragments of the nanosecond and low intensity femtosecond spectra are highlighted. In addition, as the laser intensity increases, it is observed that fragmentation pathways preferentially switch from CmH3+ ion yield to Cm+ production for m=2-5 at a critical intensity which is molecule dependent.