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

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.

Graphical abstractQuantum Theory of Atoms-in-Molecules bond critical point and delocalisation index metrics are calculated for a range of actinide-element bonds in gas-phase, continuum solvent and via an electrostatic embedded cluster approach.Figure optionsDownload full-size imageDownload as PowerPoint slide