1s2p RIXS Calculations for 3d Transition Metal Ions in Octahedral Symmetry

Zimmermann, P.; Hunault, Myrtille O.J.Y.; Groot, Frank M. F. de

doi:10.1155/2018/3618463

Cited by 8 publications

(7 citation statements)

References 46 publications

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“…In the crystal-field multiplet theory, ,,,, the local model requires the description of all the energy contributions including H SO (SO interaction) and the crystal-field multiplet Hamiltonian HCF (e.g., refer to Zimmermann et al). They are all naturally included in our ab initio approach as outlined above.…”

Section: Methodsmentioning

confidence: 99%

Relativistic MulticonfigurationalAb InitioCalculation of Uranyl 3d4f Resonant Inelastic X-ray Scattering

et al. 2021

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We applied relativistic multiconfigurational all-electron ab initio calculations including the spin–orbit interaction to calculate the 3d4f resonant inelastic X-ray scattering (RIXS) map (3d 3/2 → 5f 5/2 U M 4 absorption edge and 4f 5/2 → 3d 3/2 U M β emission) of uranyl (UO 2 2+ ). The calculated data are in excellent agreement with experimental results and allow a detailed understanding of the observed features and an unambiguous assignment of all involved intermediate and final states. The energies corresponding to the maxima of the resonant emission and the non-resonant (normal) emission were determined with high accuracy, and the corresponding X-ray absorption near edge structure spectra extracted at these two positions were simulated and agree well with the measured data. With the high quality of our theoretical data, we show that the cause of the splitting of the three main peaks in emission is due to the fine structure splitting of the 4f orbitals induced through the trans di-oxo bonds in uranyl and that we are able to obtain direct information about the energy differences between the 5f and 4f orbitals: Δ5f δ/ϕ – 4f δ/ϕ, Δ5f π* – 4f π, and Δ5f σ* – 4f σ from the 3d4f RIXS map. RIXS maps contain a wealth of information, and ab initio calculations facilitate an understanding of their complex structure in a clear and transparent way. With these calculations, we show that the multiconfigurational protocol, which is nowadays applied as a standard tool to study the X-ray spectra of transition metal complexes, can be extended to the calculation of RIXS maps of systems containing actinides.

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Section: Methodsmentioning

confidence: 99%

Relativistic MulticonfigurationalAb InitioCalculation of Uranyl 3d4f Resonant Inelastic X-ray Scattering

et al. 2021

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“…The 2p3d RIXS planes corresponding to the 2p → 4f absorption and 3d → 2p emission transitions were calculated with the multiplet theory as implemented in the Quanty library − using the input files generated by the Crispy graphical user interface . We have used an atomic representation to describe each system, that is, we did not include the effect of the coordinating atoms.…”

Section: Experimental and Theoretical Detailsmentioning

confidence: 99%

HERFD-XANES and RIXS Study on the Electronic Structure of Trivalent Lanthanides across a Series of Isostructural Compounds

et al. 2022

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We performed a systematic study of the complexes of trivalent lanthanide cations with the hydridotris(1-pyrazolyl)borato (Tp) ligand (LnTp 3 ; Ln = La, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, and Lu) using both high-energy-resolution fluorescence-detected X-ray absorption near-edge structure (HERFD-XANES) and resonant inelastic X-ray scattering (RIXS) at the lanthanide L 3 absorption edge. Here, we report the results obtained and we discuss them against calculations performed using density functional theory (DFT) and atomic multiplet theory. The spectral shape and the elemental trends observed in the experimental HERFD-XANES spectra are well reproduced by DFT calculations, while the pre-edge energy interval is better described by atomic multiplet theory. The RIXS data show a generally rather complex pattern that originates from the intra-atomic electron–electron interactions in the intermediate and final states, as demonstrated by the good agreement obtained with calculations using an atomic-only model of the absorber. Guided by theoretical predictions, we discuss the possible origins of the observed spectral features and the trends in energy splitting across the series. The insight into the electronic structure of trivalent lanthanide compounds demonstrated here and obtained with advanced X-ray spectroscopies coupled with theoretical calculations can be applied to any lanthanide-bearing compound and be of great interest for all research fields involving lanthanides.

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“…In this section, we examine the performance of X2C-MRPT2 in predicting the splitting of the 2 Π state of molecular monohydrides (GeH and SnH) and the multistate potential energy curves of the TlH dissociation pathway. The multielectronic term symbols for molecular monohydrides can be derived according to the interplay between the C ∞ v point group symmetry and the spin–orbit coupling. , …”

Section: Resultsmentioning

confidence: 99%

Exact-Two-Component Relativistic Multireference Second-Order Perturbation Theory

Jenkins

et al. 2022

J. Chem. Theory Comput.

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As the relativistic corrections become stronger for laterow elements, the fully perturbative treatment of spin−orbit coupling and dynamic correlation may become inadequate for accurate descriptions of chemical properties. In this work, we introduce a determinant-based Kramers-unrestricted exact-two-component multireference second-order perturbation (X2C-MRPT2) method which variationally includes relativistic corrections with a perturbative dynamic correlation. The restricted active space partitioning scheme is employed to provide an adjustable correlation space for the secondorder perturbation treatment. The multistate perturbation theory is also developed to improve the descriptions of ground and excited states. Benchmark studies of atomic fine-structure splittings and spectroscopic constants of molecular monohydrides using X2C-MRPT2 are compared to the other perturbative and variational approaches. The results suggest that X2C-MRPT2 is a highly accurate alternative to the fully variational multireference configuration interaction method at only a small fraction of the computational cost.

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1s2p RIXS Calculations for 3d Transition Metal Ions in Octahedral Symmetry

Cited by 8 publications

References 46 publications

Relativistic MulticonfigurationalAb InitioCalculation of Uranyl 3d4f Resonant Inelastic X-ray Scattering

Relativistic MulticonfigurationalAb InitioCalculation of Uranyl 3d4f Resonant Inelastic X-ray Scattering

HERFD-XANES and RIXS Study on the Electronic Structure of Trivalent Lanthanides across a Series of Isostructural Compounds

Exact-Two-Component Relativistic Multireference Second-Order Perturbation Theory

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