Should environmental effects be included when performing QTAIM calculations on actinide systems? A comparison of QTAIM metrics for Cs2UO2Cl4, U(Se2PPh2)4 and Np(Se2PPh2)4 in gas phase, COSMO and PEECM

Joseph P.W. Wellington, Andrew Kerridge, Nikolas Kaltsoyannis

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    Abstract

    Quantum Theory of Atoms-in-Molecules bond critical point and delocalisation index metrics are calculated for the actinide-element bonds in Cs2UO2Cl4, U(Se2PPh2)4 and Np(Se2PPh2)4, in gas-phase, continuum solvent (COSMO) and via the periodic electrostatic embedded cluster method. The effects of the environment are seen to be very minor, suggesting that they do not account for the differences previously observed between the experimental and theoretical QTAIM ρb and ∇2ρb for the U–O bonds in Cs2UO2Cl4. With the exception of the local density approximation, there is only a small dependence of the QTAIM metrics on the exchange–correlation functional employed.
    Original languageEnglish
    Pages (from-to)57–63
    JournalPolyhedron
    Volume116
    Early online date5 Mar 2016
    DOIs
    Publication statusPublished - 25 Sept 2016

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