Detection of transient fluorine atoms

Abstract

A KrF excimer laser with a fluence of 50 mJ/cm2 was used to photolyze either uranium hexafluoride or molecular fluorine, yielding a transient number density of fluorine atoms. The rise and decay of the atomic fluorine density was observed by transient absorption of a 404-cm−1 Pb-salt diode laser, which corresponds to the 2P3/2 → 2P1/2 spin-orbital transition in atomic fluorine. To prevent the diode laser wavelength from drifting out of resonance with the atomic fluorine line, part of the beam was split off and sent through a microwave discharge fluorine atom cell. This allowed a wavelength modulation-feedback technique to be used to lock the diode laser wavelength onto the atomic line. The remaining diode laser beam was made collinear with the excimer laser beam using a LiF window with a 45° angle of incidence to reflect the infrared beam while transmitting most of the UV beam. Using this setup along with a transient digitizer to average between 100 and 200 transient absorption profiles, fluorine atom number densities of the order of 1014/cm−3 in a 3-m path length were detected. The signals observed were about a factor of 5 less than expected from known photolysis cross sections.