Structure of the complex U[Cl.sub.4] x 2DMF by vibrational infrared spectroscopy and density functional theory

Structural models are designed and spectral characteristics are computed based on DFT calculations for a complex of U[Cl.sub.4] with two molecules of DMF (U[Cl.sub.4] x 2DMF). The calculations were carried out using a B3LYP hybrid functional in the LANL2DZ effective core potential approximation for...

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Bibliographic Details
Published inJournal of applied spectroscopy Vol. 79; no. 1; pp. 22 - 30
Main Authors Shundalau, M.B, Komyak, A.I, Zazhogin, A.P, Umreiko, D.S
Format Journal Article
LanguageEnglish
Published Springer 01.03.2012
Subjects
Dimethylformamide
Infrared spectroscopy
Specific gravity
Uranium
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Summary:Structural models are designed and spectral characteristics are computed based on DFT calculations for a complex of U[Cl.sub.4] with two molecules of DMF (U[Cl.sub.4] x 2DMF). The calculations were carried out using a B3LYP hybrid functional in the LANL2DZ effective core potential approximation for the uranium atom and an all-electron basis set, cc-pVDZ, for all other atoms with partial force-field scaling. Two structural variants were found for the complex. The first structure is more stable, has [C.sub.i] symmetry, and is characterized by trans arrangement of ligands. The energy of the second structure of [C.sub.2] symmetry (with cis arrangement of ligands) is greater by 46 kJ/mol. The formation of the complex is shown to be accompanied by significant changes in the structure of U[Cl.sub.4]. The obtained spectral characteristics are analyzed and compared with experimental data. The adequacy of the proposed models and the agreement between calculation and experiment are demonstrated.
ISSN:0021-9037
1573-8647