Ultrafast Transient Absorption Spectroscopy of UO22+and [UO2Cl]+

被引：8

作者：

Haubitz, Toni ^{[1
]}

Tsushima, Satoru ^{[2
,3
]}

Steudtner, Robin ^{[2
]}

Drobot, Bjorn ^{[4
]}

Geipel, Gerhard ^{[2
]}

Stumpf, Thorsten ^{[2
]}

Kumke, Michael U. ^{[1
]}

机构：

[1] Univ Potsdam, Inst Chem, Karl Liebknecht Str 24-25, D-14476 Potsdam, Germany

[2] Helmholtz Zentrum Dresden Rossendorf, Inst Resource Ecol, Bautzner Landstr 400, D-01328 Dresden, Germany

[3] Tokyo Inst Technol, Inst Innovat Res, Tokyo Tech World Res Hub Initiat WRHI, Tokyo 1528550, Japan

[4] Max Planck Inst Mol Cell Biol & Genet, Pfotenhauerstr 108, D-01307 Dresden, Germany

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2018年 / 122卷 / 35期

关键词：

LASER-INDUCED FLUORESCENCE; ELECTRON-TRANSFER; AQUEOUS-SOLUTION; URANYL COMPLEXES; EXCITED-STATES; URANIUM(VI); SPECIATION; MECHANISM; LUMINESCENCE; ION;

D O I：

10.1021/acs.jpca.8b05567

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

For the only water coordinated "free" uranyl (VI) aquo ion in perchlorate solution we identified and assigned several different excited states and showed that the (3)Delta state is the luminescent triplet state from transient absorption spectroscopy. With additional data from other spectroscopic methods (TRLFS, UV/vis) we generated a detailed Jablonski diagram and determined rate constants for several state transitions, like the inner conversion rate constant from the (3)Phi state to the (3)Delta state transition to be 0.35 ps(-1). In contrast to luminescence measurements, it was possible to observe the highly quenched uranyl(VI) ion in highly concentrated chloride solution by TAS and we were able to propose a dynamic quenching mechanism, where chloride complexation is followed by the charge transfer from the excited state uranyl(VI) to chloride. This proposed quenching route is supported by TD-DFT calculations.

引用

页码：6970 / 6977

页数：8

共 32 条

[31] Cryogenic laser induced fluorescence characterization of U(VI) in hanford vadose zone pore waters [J].