Abstract
Herein we show that non-resonant inelastic x-ray scattering involving an $s$ core level is a powerful spectroscopic method to characterize the excited states of transition metal compounds. The spherical charge distribution of the $s$ core hole allows the orientational dependence of the intensities of the various spectral features to produce a spatial charge image of the associated multiplet states in a straightforward manner, thereby facilitating the identification of their orbital character. In addition, the $s$ core hole does not add an extra orbital angular momentum component to the multiplet structure so that the well-established Sugano-Tanabe-Kamimura diagrams can be used for the analysis of the spectra. For $\alpha$-MnS we observe the spherical charge density corresponding to its high spin $3d^5$ ($^6A_1$) ground state configuration and we were able to selectively image its excited states and identify them as $t_{2g}$ ($^5T_2$) and $e_g$ ($^5E$) with an energy splitting $10Dq$ of 0.78\,eV.
Highlights
We show that nonresonant inelastic x-ray scattering involving an s core level is a powerful spectroscopic method to characterize the excited states of transition metal compounds
The s core hole does not add an extra orbital angular momentum component to the multiplet structure so that the well-established SuganoTanabe-Kamimura diagrams can be used for the analysis of the spectra
We have shown that nonresonant inelastic x-ray scattering (NIXS, known as x-ray Raman scattering) involving an s core hole (s-NIXS) is an experimental method that can provide a direct image of the local d hole density in transition metal oxide single crystals [2,3]; i.e., the ground state d orbital can be determined without the need for calculations to interpret the spectral line shape
Summary
The well-established and readily available Sugano-TanabeKamimura diagrams that depict the multiplet energy scheme of 3d ions for varying values of the crystal field [4]. As explained earlier [2], given that the core-level s orbital is spherical, the directional dependence of the integrated M1 intensity is only determined by (and directly proportional to) the density of d holes in the direction parallel to q. In other words, this directional dependence provides a direct spatial image of the local empty valence states. The excitation into eg orbitals is represented by c100ðΘÞ, the weight of the Sqk100 component peaking at 83.15 eV The difference between these two energies is due to the eg − t2g splitting, and it is a direct measurement of the crystal field parameter 10Dq 1⁄4 83.15 eV–82.37 eV 1⁄4 0.78 eV. Sd · Ss can be obtained by inverting the formula [13] ðStotÞ2 1⁄4 ðSdÞ2 þ ðSsÞ2 þ 2Sd · Ss, where Stot can be Sd þ
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