Ionization and Dissociation of Benzaldehyde Using Short Intense Laser Pulses

In a recent series of experiments, femtosecond laser mass spectrometry (FLMS) was applied to benzaldehyde utilizing laser pulse widths in the range 90 fs to 2.7 ps. Beam intensities up to 2 × 10 14 W cm -2 were used with wavelengths of 750 and 375 nm. Different ionization−dissociation channels were found compared with previous studies by other authors based in the nanosecond regime. The general theme emerging is one of predominant above-threshold ionization−dissociation (ID) in which predissociative states are largely bypassed via rapid optical up-pumping to the molecular ionization continuum. Above the parent ionization threshold, ladder-switching is seen to be a function of laser pulse width, intensity, and wavelength with exclusive parent ion formation being achievable in the lower intensity regions at all pulse widths. Increasing fragmentation occurs as the laser intensity increases, although parent supremacy remains. At 750 nm however, the increase of fragmentation with intensity is greatly reduced compared to 375 nm, leading to the conclusion that FLMS at longer wavelengths is preferred for chemical analysis. Moreover at 750 nm and at laser intensities close to 10 14 W cm -2 C 7 H 6 O 2+ becomes evident. It is also shown that the C 7 H 6 O + /C 7 H 5 O + ratio is strongly dependent on the pulse width, suggesting that a hydrogen loss pathway has a dissociation time of about a picosecond.