How accurate are electronic structure methods for actinoid chemistry?

Dissecting the cation–cation interaction between two uranyl units

“…11,41 Yet, single-reference methods such as density functional theory (DFT) and unrestricted coupled cluster can handle these types of quasi-degeneracies reasonably well, providing acceptably good results for uranyl(V) compounds. 13,17,[46][47][48][49][50][51][52][53] These findings paved the way for computational studies of larger, more realistic uranyl-containing complexes and clusters, for which reasonable agreement with experimental data could be achieved. 13,17,[46][47][48][49][50][51][52][53] These findings paved the way for computational studies of larger, more realistic uranyl-containing complexes and clusters, for which reasonable agreement with experimental data could be achieved.…”

Theoretical study of the electronic spectra of neutral and cationic NpO and NpO2

“…41 The goal of the present study is the systematic evaluation of the gas-phase electronic spectra of the neutral and ionic NpO and NpO 2 species by means of multireference relativistic ab initio calculations on the basis of our previous studies on the electronic ground states of these species. 12,38 Other important results from the present calculations are the energies of the excited states, required for a reliable evaluation of the thermodynamic functions of the gaseous oxides. Such thermodynamic data are utilized in developing safety procedures in nuclear industry.…”

“…Several computational studies were performed on neutral and ionic neptunium mono-and dioxides at SO-CASPT2 and various DFT levels resulting in theoretical ionization energies, 12,38 vibrational frequencies, 13 and dissociation energies. 38,39 The hydration and oxidation reactions of NpO 2 + in the gaseous phase were studied by DFT assisting electrospray experiments, 40 while NpO 2 2+ served as model compound (focusing on the bond distance and vibrational frequencies) in a benchmark study of two-component relativistic DFT methods. 41 The goal of the present study is the systematic evaluation of the gas-phase electronic spectra of the neutral and ionic NpO and NpO 2 species by means of multireference relativistic ab initio calculations on the basis of our previous studies on the electronic ground states of these species.…”

“…12,19,[23][24][25][26][29][30][31][32][33][34][35]38,39 We computed the excited electronic states up to ca. 35 000 cm −1 using the SO-CASPT2 method.…”

Relativistic Pseudopotentials and Their Applications

“…By applying different density functionals together with PPs to actinoids Averkiev et al [105] have found that MPW3LYP, B3LYP, M06, and M05 produced as accurate or even more accurate bond energies and IPs than AE complete active space second-order perturbation theory (CASPT2), CCSD, and CCSD(T) methods. Kovács et al [106] evaluated trends in the bond distances and dissociation enthalpies of AnO and AnO 2 (An = Th-Lr) at the DFT level and demonstrated the very good performance of the B3LYP exchange-correlation functional in conjunction with SPPs.…”