Pulsed photothermal spectroscopy applied to lanthanide and actinide speciation

摘要

Abstract: Several key elements important for the application oflaser-based photothermal spectroscopies to the study ofthe complexation chemistry of lanthanides and actinidesin solution have been demonstrated. The sensitivity off-f electronic transition energies and band intensitiesto subtle changes in complexation is illustratedthrough comparison of visible and near infra-redabsorption spectra of well-characterized U(IV) dimerswith alkoxide ligands. Significant improvements inspectroscopic band resolution and energy measurementprecision for solution species are shown to beachievable through work in frozen glasses at 77 K usinga very simple cryogenic apparatus. A pulsed-laserphotothermal spectroscopy apparatus was constructed andshown to be sensitive to optical density changes of10$+$MIN@5$/ in an aqueous Nd$+3$PLU$/ solution. Inaddition, the capability of obtaining photothermallensing spectra of dilute actinide solutions in frozenglasses at 77 K is demonstrated.!