Theoretical study of the microhydration of mononuclear and dinuclear uranium(VI) species derived from solvolysis of uranyl nitrate in water
✍ Scribed by Milan Ončák; Detlef Schröder; Petr Slavíček
- Publisher
- John Wiley and Sons
- Year
- 2010
- Tongue
- English
- Weight
- 822 KB
- Volume
- 31
- Category
- Article
- ISSN
- 0192-8651
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✦ Synopsis
The structures and energetics of mononuclear and dinuclear uranium species formed upon speciation of uranyl(VI) nitrate, UO 2 (NO 3 ) 2 , in water are investigated by quantum chemistry using density functional theory and the wavefunction-based methods (MP2, CCSD, CCSD(T)). We provide a discussion of the basic coordination patterns of the various mono-and dinuclear uranyl compounds [(UO 2 ) m (X,Y) 2m21 (H2O) n ] 1 (m 5 1, 2; n 5 0-4) found in a recent mass spectrometric study (Tsierkezos et al., Inorg Chem 2009, 48, 6287). The energetics of the complexation of the uranyl dication to the counterions OH 2 and NO 3 2 as well as the degradation of the dinuclear species were studied by reference to a test set of 16 representative molecules with the MP2 method and the B3LYP, M06, M06-HF, and M06-2X DFT functionals. All DFT functionals provide structures and energetics close to MP2 results, with M06 family being slightly superior to the standard B3LYP functional.