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

Crystallographic structure and crystal field parameters in the [AnIV(DPA)3]2− series, An = Th, U, Np, Pu

“…there is a depletion of the charge density at the BCP of each M-O and M-N interaction. Hence, all those values show a ionic or donor-acceptor type interaction, in accordance with previous QTAIM analysis on actinide complexes [25,19,101,26]. The ionic nature of the M-O and M-N bonds is also supported by the computed QTAIM charges, which reflect highly polarized bonds.…”

“…This approach analyzes the topology of the electron density, the purpose being to answer questions about the chemical bonding and the chemical reactivity. The QTAIM has been successfully applied to actinide complexes described at the DFT level [25,26]. In this work, the [An IV (DPA) 3 ] 2complexes are described by the SO-CASPT2 method, and the bonding between the actinide ion and the coordinating atoms is characterized using the QTAIM.…”

Charge densities in actinide compounds: strategies for data reduction and model building

“…The adequacy of these results can be confirmed by topological analysis of the resulting total ground-state electron density and by comparison with results derived from theoretical charge densities in the context of Bader's Quantum Theory of Atoms in Molecules (QTAIM) (Bader, 1994). Experimentally determined bond descriptors are in fair agreement with those obtained from high-level theoretical calculations (Tanti et al, 2018;Gianopoulos et al, 2017b;Wellington et al, 2016), although theoretical results may show a dependence on the methods applied (Schreckenbach & Shamov, 2010).…”

Ionic adsorption on the brucite (0001) surface: A periodic electrostatic embedded cluster method study

“…In this case, the use of an ECP region is complicated, in that we do not wish to apportion formal charges to the O and H atoms in the covalently bound OH units. Therefore, to avoid the artificial polarisation effect of neighbouring PCs on the QM cluster, we decided to employ natural charges in the PC region, 68 derived iteratively from natural population analysis (NPA). 69 Formal charges were used as an initial guess for the embedding array in a single point calculation, from which a new set of NPA charges For every s block ion investigated in section 3.1 (Na + , Rb + , Cs + and Mg 2+ , Sr 2+ , Ba 2+ ), the def2-SVP basis set 65,66,70 was used during the geometry optimisation along with the associated effective core potentials 71 for Rb, Cs, Sr and Ba.…”