Relativistic theoretical studies on hydrogen bonds and the electronic structure of aqueous solvated bis(uranyl) complex: an insight into explicit and/or implicit solvent effects期刊界 All Journals 搜尽天下杂志传播学术成果专业期刊搜索期刊信息化学术搜索

Relativistic theoretical studies on hydrogen bonds and the electronic structure of aqueous solvated bis(uranyl) complex: an insight into explicit and/or implicit solvent effects

Authors:

Yuan-Ru Guo Xin Zhou Qing-Jiang Pan

Institution:

1. Key Laboratory of Bio-based Material Science and Technology of Education Ministry, College of Material Science and Engineering, Northeast Forestry University, Harbin, 150040, China
3. Institute of Theoretical and Simulation Chemistry, Academy of Fundamental and Interdisciplinary Science, Harbin Institute of Technology, Harbin, 150008, China
2. Key Laboratory of Functional Inorganic Material Chemistry of Education Ministry, School of Chemistry and Materials Science, Heilongjiang University, Harbin, 150080, China

Abstract:

To understand the chemical behavior of uranyl complexes in water, a bis-uranyl (phen)(UO₂)(μ₂–F)(F)]₂ (A; phen?=?phenanthroline, μ₂?=?doubly bridged) and its hydrated form A?·?(H₂O)_n (n?=?2, 4 and 6) were examined using scalar relativistic density functional theory. The addition of water caused the phen ligands to deviate slightly from the U₂(μ₂–F)₂ plane, and red-shifts the U–F-terminal and U?=?O stretching vibrations. Four types of hydrogen bonds are present in the optimized hydrated A?·?(H₂O)_n complexes; their energies were calculated to fall within the range 4.37–6.77 kcal mol^-1, comparable to the typical values of 5.0 kcal mol^-1 reported for hydrogen bonds. An aqueous environment simulated by explicit and/or implicit models lowers and re-arranges the orbitals of the bis-uranyl complex.

Figure
A bis(uranyl) complex (phen)(UO₂)(μ₂–F)(F)]₂ (A) and its solvated form A?·?(H₂O)_n were examined using scalar relativistic density functional theory. Hydrogen bonds cause the phen ligand to slightly deviate from the equatorial plane of the uranyl ion, resulting in a pronounced red-shift of the U–F-terminal and U?=?O asymmetric stretching vibrations. The calculated energies fall within 4.4?–6.8 kcal/mol. Explicit and/or implicit aqueous solvation re-arranges the molecular orbitals of the complex

Keywords:

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