Theoretical Study of the Substituent and Nitrogen Number Effects on the Uranium Binding Selectivity of Crown Ethers

The compounds, [UO2(dibenzo-18-crown-6)]2+ and [UO2(18-crown-6)]2+, as well as their related complexes: numerous disubstituted dibenzo-18-crown-6 and azacrown complexes are studied using density functional theory (DFT). Quasi-relativistic effective core potentials developed in the Stuttgart and Dresden groups was used together with the accompanying basis set for uranium and DZP basis set was used for crown ether atoms. The effects of substituent and nitrogen number on the binding selectivity were discussed in term of the structural parameter, atomic charge and interaction energy, thermodynamic parameters, and charge transfer. The electron donating substituents increase the capability of dibenzo-18-crown-6 toward UO22+ ion. In contrast, the electron withdrawing substituents have the opposite effect. It clearly shows that UO22+ prefers N donor recognition. For the systems involved, the result shows that the hexaaza-18-crown-6 exhibits the largest metal interaction capability to UO22+ ion. The calculated results are in a good agreement with the experimental values.

Halogen and Hydrogen Bonding in Halogenabenzene/NH3 Complexes Compared Using Next-Generation QTAIM

Next-generation quantum theory of atoms in molecules (QTAIM) was used to investigate the competition between hydrogen bonding and halogen bonding for the recently proposed (Y = Br, I, At)/halogenabenzene/NH3 complex. Differences between using the SR-ZORA Hamiltonian and effective core potentials (ECPs) to account for relativistic effects with increased atomic mass demonstrated that next-generation QTAIM is a much more responsive tool than conventional QTAIM. Subtle details of the competition between halogen bonding and hydrogen bonding were observed, indicating a mixed chemical character shown in the 3-D paths constructed from the bond-path framework set B. In addition, the use of SR-ZORA reduced or entirely removed spurious features of B on the site of the halogen atoms.

The Geometries and Stabilities of Neutral and Anionic Vanadium Doped Germanium Clusters VGen0/-( n = 9 - 13): Density Functional Theory Investigations

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