Journal article
Thermodynamic and structural features of aqueous Ce(III)
The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.112(44), pp.11198-11206
11/06/2008
Handle:
https://hdl.handle.net/2376/114512
PMID: 18844331
Abstract
With a single f-electron, Ce(III) is the simplest test case for benchmarking the thermodynamic and structural properties of hydrated Ln(III) against varying density functionals and reaction field models, in addition to determining the importance of multiconfigurational character in their wave functions. Here, the electronic structure of Ce(H2O)x(H 2O)y(3+) (x = 8, 9; y = 0, 12-14) has been examined using DFT and CASSCF calculations. The latter confirmed that the wave function of octa- and nona-aqua Ce(III) is well-described by a single configuration. Benchmarking was performed for density functionals, reaction field cavity types, and solvation reactions against the experimental free energy of hydration, DeltaG(hyd)(Ce(3+)). The UA0, UAKS, Pauling, and UFF polarized continuum model cavities displayed different performance, depending on whether one or two hydration shells were examined, and as a function of the size of the metal basis set. These results were essentially independent of the density functional employed. Using these benchmarks, the free energy for water exchange between CN = 8 and CN = 9, for which no experimental data are available, was estimated to be approximately -4 kcal/mol.
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Details
- Title
- Thermodynamic and structural features of aqueous Ce(III)
- Creators
- Adriana Dinescu - Idaho National Laboratory, P.O. Box 1625, Idaho Falls, Idaho 83415-2208, USAAurora E Clark
- Publication Details
- The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol.112(44), pp.11198-11206
- Academic Unit
- Chemistry, Department of
- Publisher
- United States
- Identifiers
- 99900547861901842
- Language
- English
- Resource Type
- Journal article