LFDFT—A Practical Tool for Coordination Chemistry

Abstract

The electronic structure of coordination compounds with lanthanide ions is studied by means of density functional theory (DFT) calculations. This work deals with the electronic structure and properties of open-shell systems based on the calculation of multiplet structure and ligand-field interaction, within the framework of the Ligand–Field Density-Functional Theory (LFDFT) method. Using effective Hamiltonian in conjunction with the DFT, we are able to reasonably calculate the low-lying excited states of the molecular [Eu(NO3)3(phenanthroline)2] complex, subjected to the Eu3+ configuration 4f6. The results are compared with available experimental data, revealing relative uncertainties of less than 5% for many energy levels. We also demonstrate the ability of the LFDFT method to simulate absorption spectrum, considering cerocene as an example. Ce M4,5 X-ray absorption spectra are simulated for the complexes [Ce(η8−C8H8)2] and [Ce(η8−C8H8)2][Li(tetrahydrofurane)4], which are approximated by the Ce oxidation states 4+ and 3+, respectively. The results showed a very good agreement with the experimental data for the Ce3+ compound, unlike for the Ce4+ one, where charge transfer electronic structure is still missing in the theoretical model. Therefore this presentation reports the benefits of having a theoretical method that is primarily dedicated to coordination chemistry, but it also outlines limitations and places the ongoing developmental efforts in the broader context of treating complex molecular systems.

U(V) Stabilization via Aliovalent Incorporation of Ln(III) into Oxo‐salt Framework

“…The U M 4 ‐edge XAS spectra were calculated using the ligand‐field density‐functional theory (LFDFT) method [43–44] . All calculations were done by using the hybrid Perdew‐Burke‐Ernzerhof PBE0 functional [45] .…”

“…The U M 4 -edge XAS spectra were calculated using the ligand-field density-functional theory (LFDFT) method. [43][44] All calculations were done by using the hybrid Perdew-Burke-Ernzerhof PBE0 functional. [45] Molecular orbitals were expanded by means of the allelectron Slater-type orbitals basis set of quadrupole-zeta augmented by four sets of polarization function (QZ4P) for all elements.…”

Probing the Subtle Differences between Promethium and Curium

“…To aid the interpretation of the promethium absorption and emission spectra, the ligand-eld DFT (LFDFT) approximation 33 was considered using the same level of theory as in the single point calculations. Within LFDFT, the multiplet structure for an f n electron con guration is calculated using the Kohn-Sham orbitals obtained from an average of con guration (AOC) calculation.…”

Dedication: Commemorative Issue in Honor of Professor Karlheinz Schwarz on the Occasion of His 80th Birthday

“…We can notice the large panel of scientific topics covered by Karlheinz's knowledge. We deeply acknowledge the following contributions related to spectroscopy by Manuel Yañez et al [12], Juan-Carlos Sancho-García and Emilio San-Fabián [13]; excited states by Ágnes Nagy [14], Kalidas Sen et al [15] and Fabrizia Negri et al [16]; DFT developments by Fabio Della Sala et al [17], Mathias Rapacioli and Nathalie Tarrat [18], Emmanuel Fromager et al [19], José Manuel García de la Vega et al [20] and Harry Ramanantoanina [21]; results analysis by Andreas Savin et al [22] and Manuel Richter et al [23]; and, of course, the solid state and surfaces by Leila Kalantari and Fabien Tran et al [24], Denis Salahub et al [25], Peter Blaha et al [26], Samuel B. Trickey [27], William Lafargue-Dit-Hauret and Xavier Rocquefelte [28], Tzonka Mineva and Hazar Guesmi et al [29]. (H.C.)…”