Structure of a uranyl peroxo complex in aqueous solution from first-principles molecular dynamics simulations.
Structure of a uranyl peroxo complex in aqueous solution from first-principles molecular dynamics simulations.
复制标题
根据第一原理分子动力学模拟得出水溶液中过氧化铀络合物的结构。
作者：
M. Bühl;N. Sieffert;G. Wipff
本文报道了[UO_2（OH）（κ（2）-O_2）（H_2 O）_2]（-）和[UO_2（OH）_2（κ（1）-O_2 H）（H_2 O）]（-）的静态从头算和密度泛函计算，以及水溶液中的Car-Parrinello分子动力学模拟。而κ（1）-氢过氧异构体在气相中比κ（2）-过氧形式更稳定，在显式本体溶液中稳定性顺序相反。基于来自热力学积分（BLYP泛函）的自由能，过氧形式受到ca. 32 kJ mol（-1）的水溶液。这种稳定讨论的水化壳的有关的个别配体和在水中的配合物的偶极矩，并突出了明确的溶质-溶剂相互作用和散装溶剂化的铀酰（VI）化合物的形态的重要性。
Static ab initio and density-functional computations, as well as Car-Parrinello molecular dynamics simulations in aqueous solution are reported for [UO2(OH)(κ(2)-O2)(H2O)2](-) and [UO2(OH)2(κ(1)-O2H)(H2O)](-). Whereas the κ(1)-hydroperoxo isomer is found to be more stable than the κ(2)-peroxo form in the gas phase, the order of stability is reversed in explicit bulk solution. Based on free energies from thermodynamic integration (BLYP functional), the peroxo form is favoured by ca. 32 kJ mol(-1) in water. This stabilisation is discussed in terms of the hydration shells about the individual ligands and dipole moments of the complexes in water, and highlights the importance of explicit solute-solvent interactions and bulk solvation for the speciation of uranyl(vi) compounds.
影响因子：
3.3
作者：
Brehm, Martin;Weber, Henry;Kirchner, Barbara
通讯作者：
Kirchner, Barbara