Calculation of multipole transitions at the FeKpre-edge throughp-dhybridization in the Ligand Field Multiplet model

Arrio, Marie‐Anne; Rossano, Stéphanie; Brouder, Christian; Galoisy, Laurence; Calas, Georges

doi:10.1209/epl/i2000-00515-8

Cited by 74 publications

(92 citation statements)

References 18 publications

(35 reference statements)

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“…9, the transition matrix elements are not calculated in the LFM framework. This has been done for the first time in the case of the Fe K pre-edge by Arrio et al 10 More precisely, the eigenstates of the ions and the absolute intensities of the E2 and E1 transitions involved in the K pre-edge of Fe 2+ and Fe 3+ in minerals, where the iron ions are either in octahedral or tetrahedral sites, have been calculated. The LFM calculated spectra of the 3d n -1s 1 3d n+1 E2 transitions with a crystal field value 10Dq of 1.2 eV for n = 0,. .…”

Section: Overviewmentioning

confidence: 99%

First-principles calculations of X-ray absorption spectra at the K-edge of 3d transition metals: an electronic structure analysis of the pre-edge

Cabaret

Bordage

Juhin

et al. 2010

Phys. Chem. Chem. Phys.

152

151

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. First-principles calculations of X-ray absorption spectra at the K-edge of 3d transition metals: an electronic structure analysis of the pre-edge. Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2010Chemistry, , 12, pp.5619-5633. 10.1039 This paper is published as part of a PCCP themed issue on recent developments in X-ray absorption spectroscopy Complementarity between high-energy photoelectron and L-edge spectroscopy for probing the electronic structure of 5d transition metal catalysts Toyli Anniyev, Hirohito Ogasawara, Mathias P. First-principles calculations of X-ray absorption spectra at the K-edge of 3d transition metals: an electronic structure analysis of the pre-edge We first present an extended introduction of the various methods used to extract electronic and structural information from the K pre-edge X-ray absorption spectra of 3d transition metal ions. The K pre-edge structure is then modelled for a selection of 3d transition metal compounds and analyzed using first-principles calculations based on the density functional theory (DFT) in the local density approximation (LDA). The selected compounds under study are presented in an ascending order of electronic structure complexity, starting with the Ti K-edge of rutile and anatase, and finishing with the Fe K-edge of the cyanomet-myoglobin. In most cases, the calculations are compared to polarized experimental spectra. It is shown that DFT-LDA methods enable us to reproduce satisfactorily the experimental features and to understand the nature of the electronic transitions involved in the pre-edge region. The limiting aspects of such methods in modelling the core-hole electron interaction and the 3d electron-electron repulsion are also pointed out.

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Section: Overviewmentioning

confidence: 99%

First-principles calculations of X-ray absorption spectra at the K-edge of 3d transition metals: an electronic structure analysis of the pre-edge

Cabaret

Bordage

Juhin

et al. 2010

Phys. Chem. Chem. Phys.

152

151

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“…An enlarged view around the first peak of the derivative of the spectrum, based on which we estimate the energy of the absorption edge, is shown in the top-left panel. Since Fe is in a centrosymmetric environment, the pre-edge arises mainly from 1s → 3d quadrupolar transitions 18 , and is therefore particularly weak (∼ 1/50 of the intensity of the main edge). Accordingly, it is plotted separately from the main edge for visibility, in the top-right panel.…”

Section: Interpretation Of the K Edge Lineshapementioning

confidence: 99%

Charge transfer in FeOCl intercalation compounds and its pressure dependence: An x-ray spectroscopic study

et al. 2010

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We present a study of charge transfer in Na-intercalated FeOCl and polyaniline-intercalated FeOCl using high-resolution x-ray absorption spectroscopy and resonant x-ray emission spectroscopy at the Fe-K edge. By comparing the experimental data with ab-initio simulations, we are able to unambiguously distinguish the spectral changes which appear due to intercalation into those of electronic origin and those of structural origin. For both systems, we find that about 25% of the Fe sites are reduced to Fe 2+ via charge transfer between FeOCl and the intercalate. This is about twice as large as the Fe 2+ fraction reported in studies using Mössbauer spectroscopy. This discrepancy is ascribed to the fact that the charge transfer occurs on the same time scale as the Mössbauer effect itself. Our result suggests that every intercalated atom or molecule is involved in the chargetransfer process, thus making this process a prerequisite for intercalation. The Fe 2+ fraction is found to increase with pressure for polyaniline-FeOCl, hinting at an enhancement of the conductivity in the FeOCl intercalation compounds under pressure.

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“…Moreover, additional parameters are required to describe the 3d-4p orbital hybridization. 38 This makes it more complicated to apply the CTM model for complexes with little or no symmetry.…”

Section: Introductionmentioning

confidence: 99%

Simulations of iron K pre-edge X-ray absorption spectra using the restricted active space method

Guo

Sørensen

Delcey

et al. 2016

Phys. Chem. Chem. Phys.

106

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Simulations of iron K pre-edge X-ray absorption spectra using the core restricted active space method.Physical Chemistry, http://dx.doi.org/10.1039/c5cp07487hAccess to the published version may require subscription. N.B. When citing this work, cite the original published paper. Permanent link to this version:http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-243571Simulations of iron K pre-edge X-ray absorption spectra using the restricted active space method † Meiyuan Guo, a Lasse Kragh Sørensen, a Mickaël G. Delcey, a,b Rahul V. Pinjari, a,c and Marcus Lundberg * aThe intensities and relative energies of metal K pre-edge features are sensitive to both geometric and electronic structure. With the possibility to collect high-resolution spectral data it important to find theoretical methods that include all important spectral effects: ligand-field splitting, multiplet structures, 3d-4p orbital hybridization, and charge-transfer excitations. Here the restricted active space (RAS) method is used for the first time to calculate metal K pre-edge spectra of open-shell systems, and its performance is tested against six iron complexes: [FeCl 6 ] n-, [FeCl 4 ] n-, and [Fe(CN) 6 ] n-in ferrous and ferric oxidation states. The method gives good descriptions of the spectral shapes for all six systems. The mean absolute deviation for the relative energies of different peaks is only 0.1 eV. For the two systems that lack centrosymmetry [FeCl 4 ] 2-/1-, the ratios between dipole and quadrupole intensity contributions are reproduced with an error of 10%, which leads to good descriptions of the integrated pre-edge intensities. To gain further chemical insight, the origins of the pre-edge features have been analyzed with a chemically intuitive molecular orbital picture that serves as a bridge between the spectra and the electronic structures. The RAS method can thus be used to predict and rationalize the effects of changes in both oxidation state and ligand environment in a number of hard X-ray studies of small and medium-sized molecular systems.

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Calculation of multipole transitions at the FeKpre-edge throughp-dhybridization in the Ligand Field Multiplet model

Cited by 74 publications

References 18 publications

First-principles calculations of X-ray absorption spectra at the K-edge of 3d transition metals: an electronic structure analysis of the pre-edge

First-principles calculations of X-ray absorption spectra at the K-edge of 3d transition metals: an electronic structure analysis of the pre-edge

Charge transfer in FeOCl intercalation compounds and its pressure dependence: An x-ray spectroscopic study

Simulations of iron K pre-edge X-ray absorption spectra using the restricted active space method

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