Core Excitations of Uranyl in Cs<sub>2</sub>UO<sub>2</sub>Cl<sub>4</sub> from Relativistic Embedded Damped Response Time-Dependent Density Functional Theory Calculations - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Année : 2023

Core Excitations of Uranyl in Cs2UO2Cl4 from Relativistic Embedded Damped Response Time-Dependent Density Functional Theory Calculations

Résumé

X-ray spectroscopies, by their high selectivity and sensitivity to the chemical environment around the atoms probed, provide significant insights into the electronic structures of molecules and materials. Interpreting experimental results requires reliable theoretical models, accounting for environmental, relativistic, electron correlation, and orbital relaxation effects in a balanced manner. In this work, we present a protocol for the simulation of core excited spectra with damped response time-dependent density functional theory based on the Dirac–Coulomb Hamiltonian (4c-DR-TD-DFT), in which environmental effects are accounted for through the frozen density embedding (FDE) method. We showcase this approach for the uranium M4- and L3-edges and oxygen K-edge of the uranyl tetrachloride (UO2Cl42–) unit as found in a host Cs2UO2Cl4 crystal. We have found that the 4c-DR-TD-DFT simulations yield excitation spectra that very closely match the experiment for the uranium M4-edge and the oxygen K-edge, with good agreement for the broad experimental spectra for the L3-edge. By decomposing the complex polarizability in terms of its components, we have been able to correlate our results with angle-resolved spectra. We have observed that for all edges, but in particular the uranium M4-edge, an embedded model in which the chloride ligands are replaced by an embedding potential reproduces rather well the spectral profile obtained for UO2Cl42–. Our results underscore the importance of the equatorial ligands to simulating core spectra at both uranium and oxygen edges.

Dates et versions

hal-03990050 , version 1 (15-02-2023)

Identifiants

Citer

Wilken Aldair Misael, André Severo Pereira Gomes. Core Excitations of Uranyl in Cs2UO2Cl4 from Relativistic Embedded Damped Response Time-Dependent Density Functional Theory Calculations. Inorganic Chemistry, 2023, 62, pp.11589-11601. ⟨10.1021/acs.inorgchem.3c01302⟩. ⟨hal-03990050⟩
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