Jump to main content
Jump to site search


Non-Covalent Interactions of Uranyl Complexes: A Theoretical Study

Abstract

We report a set of theoretical calculations designed to examine the potential of model uranyl complexes to participate in hydrogen- and halogen-bonding. Potential energy scans for the interaction of [UO2Cl2(H2O)3] and [UO2(NCSe)2(H2O)3] with water demonstrate that uranyl is a weak hydrogen bond acceptor, but that equatorially coordinated water is a strong hydrogen bond donor. These predictions are supported by a survey of contacts reported in the Cambridge Structural Database. At the minima of each scan, we show that the interaction energy is only weakly dependent on the choice of theoretical method, with standard density functional theory methods comparing well with coupled-cluster, MP2 and double-hybrid predictions. Geometry optimisation of a 1:1 uranyl:water complex results in a cyclic structure, in which vibrational frequencies, atoms-in-molecules and natural bond orbital analysis support the weakness of U—Oyl as acceptor. The origin of this behaviour is traced to the electronic structure of uranyl, and in particular covalency in the U—Oyl bonds resulting from donation into formally empty 5f and 6d orbitals on U.

Back to tab navigation

Supplementary files

Publication details

The article was received on 17 Apr 2018, accepted on 15 May 2018 and first published on 15 May 2018


Article type: Paper
DOI: 10.1039/C8CP02444H
Citation: Phys. Chem. Chem. Phys., 2018, Accepted Manuscript
  •   Request permissions

    Non-Covalent Interactions of Uranyl Complexes: A Theoretical Study

    J. Platts and R. J. Baker, Phys. Chem. Chem. Phys., 2018, Accepted Manuscript , DOI: 10.1039/C8CP02444H

Search articles by author

Spotlight

Advertisements