Issue 16, 2020

Simulations of valence excited states in coordination complexes reached through hard X-ray scattering

Abstract

Hard X-ray spectroscopy selectively probes metal sites in complex environments. Resonant inelastic X-ray scattering (RIXS) makes it is possible to directly study metal–ligand interactions through local valence excitations. Here multiconfigurational wavefunction simulations are used to model valence K pre-edge RIXS for three metal-hexacyanide complexes by coupling the electric dipole-forbidden excitations with dipole-allowed valence-to-core emission. Comparisons between experimental and simulated spectra makes it possible to evaluate the simulation accuracy and establish a best-modeling practice. The calculations give correct descriptions of all LMCT excitations in the spectra, although energies and intensities are sensitive to the description of dynamical electron correlation. The consistent treatment of all complexes shows that simulations can rationalize spectral features. The dispersion in the manganese(III) spectrum comes from unresolved multiple resonances rather than fluorescence, and the splitting is mainly caused by differences in spatial orientation between holes and electrons. The simulations predict spectral features that cannot be resolved in current experimental data sets and the potential for observing d–d excitations is also explored. The latter can be of relevance for non-centrosymmetric systems with more intense K pre-edges. These ab initio simulations can be used to both design and interpret high-resolution X-ray scattering experiments.

Graphical abstract: Simulations of valence excited states in coordination complexes reached through hard X-ray scattering

Supplementary files

Article information

Article type
Paper
Submitted
22 2 2020
Accepted
26 3 2020
First published
26 3 2020
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2020,22, 8325-8335

Simulations of valence excited states in coordination complexes reached through hard X-ray scattering

E. Källman, M. Guo, M. G. Delcey, D. A. Meyer, K. J. Gaffney, R. Lindh and M. Lundberg, Phys. Chem. Chem. Phys., 2020, 22, 8325 DOI: 10.1039/D0CP01003K

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