|Abstract: ||Femtosecond time-resolved photoelectron spectroscopy (fsTRPES) experiments have been used to study the photoelectron energy spectra of simple molecules since the 1980’s. Analysis of these spectra provides information about the ultrafast internal conversion dynamics of the parent ions. However, ultraviolet pulses must be used for these pump-probe experiments in order to ionize the molecules. Since current solid state lasers, such as the Ti:sapphire laser, typically produce pulses centered at 800nm, it is necessary to generate UV pulses with nonlinear frequency mixing techniques. I therefore constructed an optical setup to generate the 3rd and 4th harmonics, at 266.7nm and 200nm, respectively, of a Ti:sapphire (Ti:sa) chirped-pulse amplified (CPA) laser system that produces 35fs pulses centered at 800nm. Thin Beta-Barium Borate (β-BaB2O4 or BBO) crystals were chosen to achieve a compromise between short pulse durations and reasonable conversion efficiencies, since ultrashort pulses are quite susceptible to broadening from group velocity dispersion (GVD).
Output energies of around 11μJ and 230nJ were measured for the 266.7nm and 200nm pulses, respectively. The transform limits of the 3rd and 4th harmonic pulse lengths were calculated from their measured spectral widths. We found that the 266.7nm bandwidth was large enough to support sub-30fs pulses, and due to cutting at the lower-wavelength end of the 200nm spectrum, we calculated an upper limit of 38fs. The pulses were compressed with pairs of CaF2 prisms to compensate for dispersion introduced by transmissive optics. Two-photon absorption (TPA) intensity autocorrelations revealed fully compressed pulse lengths of 36 ± 2 fs and 42 ± 4 fs for the 3rd and 4th harmonics, respectively.|