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A new recirculating liquid-microjet photoelectron spectrometer for multiphoton ultraviolet photoelectron spectroscopy is described. A recirculating system is essential for studying samples that are only available in relatively small quantities. The reduction in background pressure when using the recirculating system compared to a liquid-nitrogen cold-trap results in a significant improvement in the quality of the photoelectron spectra. Moreover, the recirculating system results in a negligible streaming potential. The instrument design, operation, and characterization are described in detail, and its performance is illustrated by comparing a photoelectron spectrum of aqueous phenol recorded using the recirculating system with one recorded using a liquid nitrogen cold-trap.

The ultrafast dynamics of benzaldehyde upon 260, 271, 284, and 287 nm excitations have been studied by femtosecond pump-probe time-of-flight mass spectrometry. A bi-exponential decay component model was applied to fit the transient profiles of benzaldehyde ions and fragment ions. At the S2 origin, the first decay of the component was attributed to the internal conversion to the high vibrational levels of S1 state. Lifetimes of the first component decreased with increasing vibrational energy, due to the influence of high density of the vibrational levels. The second decay was assigned to the vibrational relaxation of the S1 whose lifetime was about 600 fs. Upon 287 nm excitation, the first decay became ultra-short (56 fs) which was taken for the intersystem cross from S1 to T2, while the second decay component was attributed to the vibrational relaxation. The pump-probe transient of fragment was also studied with the different probe intensity at 284 nm pump.