Anisotropic valence→core x-ray fluorescence from a [Rh(en)3][Mn(N)(CN)5]⋅H2O single crystal: Experimental results and density functional calculations

Abstract

High resolution x-ray fluorescence spectra have been recorded for emission in different directions from a single crystal of the compound ͓Rh͑en͒ 3 ͔͓Mn͑N͒͑CN͒ 5 ͔•H 2 O. The spectra are interpreted by comparison with density functional theory ͑DFT͒ electronic structure calculations. The K␤Љ line, which is strongly polarized along the Mn-N axis, can be viewed as an N(2s)→Mn(1s) transition, and the angular dependence is understood within the dipole approximation. The so-called K␤ 2,5 region has numerous contributions but is dominated by Mn(4p) and C(2s)→Mn(1s) transitions. Transition energy splittings are found in agreement with those of calculated occupied molecular orbitals to within 1 eV. Computed relative transition probabilities reproduce experimentally observed trends.

Electronic Effects in 4-Substituted Bis(imino)pyridines and the Corresponding Reduced Iron Compounds

“…57 There are three features of an XES spectrum that contain the most relevant chemical information: the Kβ’ and Kβ 1,3 lines resulting from an electric dipole allowed 3 p to 1 s transition, 58 and the Kβ 2,5 and Kβ” lines (or valence to core region, V2C) arising from a valence electron (ligand n p or n s ) to metal 1s transition. 59,60 The Kβ 1,3 (main line, ~7030-7080 eV) region is dominated by 3 p -3 d exchange correlation with some contribution from 3 p spin-orbit coupling, resulting in sensitivity towards spin state, but little sensitivity towards ligand identity. 58 A recent study with a family of iron coordination compounds, augmented with DFT calculations, has demonstrated that the V2C region (~7080-7120 eV) is relatively insensitive to changes in the Fe site symmetry, but changes in spin state and ligand identities have significant contributions to the intensities and energy distributions.…”

Simultaneous detection of electronic structure changes from two elements of a bifunctional catalyst using wavelength-dispersive X-ray emission spectroscopy and in situ electrochemistry

“…The emission energy was calibrated to the published value of 6490.4 eV (the 1st moment from the 6485 – 6495 eV region) of Mn 2 O 3 for Mn. 35 For Ni XES, the 1 st moment energy of Ni(OH) 2 was defined as 8263.7 eV, calculated from the 8248.0–8276.0 eV region. All data were collected at room temperature with an acquisition time of 60 minutes for each spectrum.…”

Hard x-ray probe to study doping-dependent electron redistribution and strong covalency inLa1−xSr1+xMnOHerrero‐Martín1, Mirone2, Fernández-Rodríguez3 et al. 2010Phys. Rev. BSelf Cite284211View full textAdd to dashboardCite

“…Hence, in case of 3p to 1s transitions in single crystals, only 3p orbitals components that are normal to k' are observed [15,25]. It follows that the k'~//n geometry probes the crystal ab-plane components while k'~⊥n contains a 50% contribution from the crystals c-axis.…”