Ionization and Dissociation Processes of Pyrrolidine in Intense Femtosecond Laser Field

Abstract

Ionization and dissociation mechanisms of pyrrolidine in intense 800 nm laser field (1013 to 1014 W/cm2) have been experimentally investigated by using a method of molecular beam and time-of-flight mass spectrometer. Singly charged parent ion and numerous fragment ions are observed in the mass spectra, which are investigated as a function of laser intensity and polarization. In order to understand the details of the ionization processes of pyrrolidine in intense femtosecond laser field, we quantitatively calculate the rate constants and ion yields by means of generalized Keldysh−Faisal−Reiss theory, and the excitation probabilities of the excited states are also calculated by using Floquet theory. The results suggest that the ionization might occur partially through the excited states of neutral pyrrolidine. Comparing with linearly polarized (LP) laser field, we observe some enhancement of fragmentation with a circularly polarized (CP) laser field above the saturation threshold intensity which might be explained by the active energies of the pyrrolidine molecular ions are different under CP and LP laser irradiated. To interpret the dissociation patterns of the pyrrolidine ions, we have used the Rice−Ramsperger−Kassel−Marcus theory with the potential surfaces obtained from the ab initio quantum chemical calculations.