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

Erik Källman; Meiyuan Guo; Mickaël G. Delcey; Drew A. Meyer; Kelly J. Gaffney; Roland Lindh; Marcus Lundberg

doi:10.1039/D0CP01003K

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

Erik Källman,^a Meiyuan Guo,

^a Mickaël G. Delcey,^a Drew A. Meyer,^b Kelly J. Gaffney,^c Roland Lindh

^de and Marcus Lundberg

*^a

Author affiliations

* Corresponding authors

^a Department of Chemistry – Ångström Laboratory, Uppsala University, S-75120 Uppsala, Sweden
E-mail: marcus.lundberg@kemi.uu.se

^b Department of Chemistry, Case Western Reserve University, Cleveland, OH 44106, USA

^c PULSE Institute, SLAC National Accelerator Laboratory, Stanford University, Menlo Park, CA 94025, USA

^d Department of Chemistry – BMC, Organic Chemistry, Uppsala University, S-75105 Uppsala, Sweden

^e Uppsala Center for Computational Chemistry (UC3), Uppsala University, P.O. Box 596, SE-751 24 Uppsala, Sweden

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.

This article is part of the themed collections: Quantum Theory: The Challenge of Transition Metal Complexes and 2020 PCCP HOT Articles

Physical Chemistry Chemical Physics

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

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

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