Femtosecond-Laser-Induced Spectroscopy - A new tool to study interactions of actinides with organic ligands


Femtosecond-Laser-Induced Spectroscopy - A new tool to study interactions of actinides with organic ligands

Geipel, G.; Bernhard, G.; Rutsch, M.

Laser induced spectroscopic methods are an excellent tool for the study of complex formation of actinides with various ligands at relatively low concentrations. Laser-induced Photoacoustic spectroscopy and Time-resolved Laser-induced Fluorescence spectroscopy are well-known methods. These methods are inappropriate for metal ions which show no change in their spectroscopic properties with complexation. In the case of organic actinide complexes it is possible to use the dependence of fluorescence of the organic ligands on actinide concentration in order to determine complex formation constants. The fluorescence lifetimes of organic ligands in aqueous solution at room temperature are below 20 ns. To study fluorescence properties of theses organic substances laser systems with ultrashort pulses are inevitable. We, therefore, have installed a femtosecond-laser-induced fluorescence spectroscopy system in our laboratory.
The lasersystem provides femtosecond laserpulses in the wavelength range from 250 nm to 10 µm and a pulse duration of 130 fs. The repetition rate is 1 kHz. The emitted fluorescence signal is detected with an intensified CCD camera, with gate width between 80 ps and 6 ns. The delay for time resolved spectra can be adjusted between 0 and 20 ns after the laser pulse with stepwidth down to 25 ps.
We validated this time-resolved laser-induced fluorescence system by studying the fluorescence behavior of salicylic acid and 5-sulfosalicylic acid at pH 4.0 as function of the uranium(VI) concentration. Using a static quenching mechanism the complex formation constants are calculated to be log KI=0.1M= -1.12 ± 0.03 for salicylic acid and log KI=0.1M= -0.67 ± 0.08 for 5-sulfosalicylic acid, respectively, assuming a 1:1 complex formation. The data from the NIST database /1/ are log KI=0.1M= -1.0 and log KI=0.1M= -0.72, respectively. For the actinides neptunium and plutonium much less data are available. Complex formation constants of various substituted benzoic acids with these actinide elements are reported.

/1/ A.E. Martel, R.M. Smith and R.J. Motekaitis: NIST Critically Selected Stability Constants of Metal
Complexes Database Version 5.0; 1998

  • Lecture (Conference)
    Migration 2001, 16.-21.09.2001, Bregenz, Österreich

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Publ.-Id: 3856