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The report on a development of advanced methods of the study of speciation and description of sorption of actinoids
Vopálka, D. ; Drtinová, B. ; Motl, A. ; Šebera, Jakub ; Štamberg, K. ; Vetešník, A. ; Višňák, J. ; Zavadilová, A.
The report of the last period of the project presents a development of three topics, each of which relates to the study of the radionuclide migration in fields near to disposal of nuclear waste and other nuclear facilities. The local structure and thermodynamic stability of uranyl sulfate complexes in aqueous solution was investigated by DFT theory. Interpretation of UV-VIS absorption spectra of uranyl-sulfate and -aqua complexes in aqueous solution was performed within the time-dependent DFT calculations. The structures were optimized in the aqueous phase at the B3LYP level by using model COSMO. The calculated geometries of aqua-sulfate complexes corresponded to the experimental data. DFT method described qualitatively thermodynamic stability of complexes in solution. TD-DFT method correctly interpreted only a part of absorption spectra (190-340 nm). In order to interpret the area around 420 nm it will be necessary to use the two-component relativistic TD-DFT.
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Modelování spektrálních a fotochemických vlastností diiminových karbonylových komplexů přechodových kovů s diiminy
Šebera, Jakub ; Záliš, Stanislav ; Vlček, Antonín
The felxibility pf the coordination sphere of mixed valence carbonyl complexes enables to tune spectral and protochemical properties. The variety of excited states in ilustrated on Ru, Re and W mixed ligand carbonyl complexed. The lowest excited states of [W(CO)4L] and [W(CO)5L’] (L=N,N'-di-methyl-1,4-diazabutadiene, ethylenediamine, 2,2’-bipyridine, phenantroline; L’= pyridine, 4-CN-pyridine, piperidine) ckomplexes were found to be either W -> pi*(L) or W -> pi*(CO) in charakter, depending on the type of the heteroligands.
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