Intrinsic deviations in fluorescence yield detected x-ray absorption spectroscopy: the case of the transition metal L<sub>2,3</sub>edges

Kurian, Reshmi; Kunnus, Kristjan; Wernet, Philippe; Butorin, Sergei M.; Glatzel, Pieter; Groot, Frank M. F. de

doi:10.1088/0953-8984/24/45/452201

Cited by 52 publications

(74 citation statements)

References 37 publications

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“…47,48 Saturation effects are negligible in the measured PFY-XAS spectra at the used solution concentrations. Spectral features in the RIXS maps can be categorized according to whether they correspond to valence excited final states resulting from filling of the corehole created by photoabsorption or whether they correspond to ionized final states resulting from fluorescence decays preceded by Coster−Kronig decays (at the Fe L2-edge).…”

Section: They Thus Correspond To Partial-fluorescence Yield (Pfy) Detmentioning

confidence: 90%

Viewing the Valence Electronic Structure of Ferric and Ferrous Hexacyanide in Solution from the Fe and Cyanide Perspectives

et al. 2016

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Abstract:The valence excited states of ferric and ferrous hexacyanide ions in aqueous solution were mapped with resonant inelastic X-ray scattering (RIXS) at the Fe L2,3-and N K-edges. Probing of both the central Fe and the ligand N atoms enabled identification of the metal-and ligand-centered excited states, as well as ligandto-metal and metal-to-ligand charge transfer excited states. Ab initio calculations utilizing the RASPT2 method was used to simulate the Fe L2,3-edge RIXS spectra and enabled quantification of the covalency of both occupied and empty orbitals of π and σ symmetry. We find that π back-donation in the ferric complex is smaller compared to the ferrous complex. This is evidenced by the relative amount of Fe 3d character in the nominally 2π CN -molecular orbital of 7% and 9% in ferric and ferrous hexacyanide, respectively. Utilizing the direct sensitivity of Fe L3-edge RIXS to the Fe 3d character in the occupied molecular orbitals we also find that the donation interactions are dominated by σ-bonding. The latter is found to be stronger in the ferric complex with a Fe 3d contribution to the nominally 5σ CN -molecular orbitals of 29% compared to 20% in the ferrous complex. These results are consistent with the notion that a higher charge at the central metal atom increases donation and decreases back-donation.

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Section: They Thus Correspond To Partial-fluorescence Yield (Pfy) Detmentioning

confidence: 90%

Viewing the Valence Electronic Structure of Ferric and Ferrous Hexacyanide in Solution from the Fe and Cyanide Perspectives

et al. 2016

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“…Corresponding partial-fluorescence yield (PFY) spectra using the same crystal filed value of 10Dq=1.8 (1.2) eV for all trivalent (divalent) ions were calculated according Ref. [22]. In short, the combination of L 2,3 -edge XAS and the following (resonant) emission or fluorescence was taken into account, or in x-ray spectroscopy terms, the 2p3d resonant inelastic x-ray scattering (RIXS) calculation was performed using the same octahedral field as for the normal XAS.…”

Section: A Crystal Field Multiplet Theorymentioning

confidence: 99%

“…Corresponding atomic PFY calculations were done with 10Dq=0 eV still according Ref. [22] (the method also shortly described above). For these atomic multiplet calculations, the effect of G pd is tested: the calculations were performed with G pd [111] and without G pd [011] while the other Slater integrals (F pd F dd ) were taken into account.…”

Section: B Atomic Multiplet Calculationsmentioning

confidence: 99%

State-dependent fluorescence yields through the core-valence Coulomb exchange parameter

2014

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Total and partial fluorescence yield (PFY) L-edge x-ray absorption spectra differ from the transmission x-ray absorption spectra (XAS) through state-dependent fluorescence yield across the XAS. For 3d1 to 3d 9 in octahedral symmetry we apply simulations of PFY and XAS and show how the atomic 2p3d Coulomb exchange parameter G pd governs the differences in the L3/(L2+L3) branching ratio between PFY and XAS. G pd orders the XAS final states following Hund's rules creating a strong state-dependent fluorescence decay strength variation across the XAS leading to the differences between PFY and XAS.

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“…X-ray optical effects, including, in general, more than the mentioned solvent-background variation and, in particular, the strong polarization dependence [7,8], are not quantitatively treated although this is necessary and straightforwardly possible [4].…”

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confidence: 99%

Comment on “State-Dependent Electron Delocalization Dynamics at the Solute-Solvent Interface: Soft-X-ray Absorption Spectroscopy and Ab Initio Calculations”

et al. 2014

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In a recent letter, Bokarev et al.[1] create a general relationship between state-dependent fluorescence yield and electron delocalization in L-edge x-ray absorption spectra based on 2p core-electron excitations into e g and t 2g orbitals for three aqueous ionic species. In this Comment, we show that Bokarev et al. do not account for previous findings and that their claims are unsubstantiated.The crucial role of state-dependent fluorescence yield was established previously [2][3][4]. Ab initio restricted active space self consistent field approaches for transition-metal L-edge spectroscopy have been reported before [5,6] and it was established that the state-dependence fluorescence yield for aqueous Cr 3þ arises from local atomic effects [4]. In contrast to the assertions in Ref.[1] that the analysis in Ref.[4] is mostly based on semiempirical simulations of spectral line shapes, we note that the same kind of ab initio quantum-chemistry model was employed as in Ref. [1]. Furthermore, rigorous ab initio calculations of the fluorescence pathways are missing in Ref.[1] although they were shown to be essential for a correct interpretation of the fluorescence-yield x-ray spectra [4].In spite of these findings and beyond the presented computational approach, Bokarev et al. advocate an interpretation in which the differences between total and partial fluorescence yield x-ray spectra arise, next to large x-ray optical effects, from a t 2g -and e g -dependent delocalization of the core-excited electron into the water solvation shell. X-ray optical effects, including, in general, more than the mentioned solvent-background variation and, in particular, the strong polarization dependence [7,8], are not quantitatively treated although this is necessary and straightforwardly possible [4].The interpretation by Bokarev et al. is based on two arguments. The first is that the covalent overlap between the oxygen 2p derived lone-pair state of water is larger with the Fe e g than with the t 2g orbitals. Second, Bokarev et al. determine the time-independent dipole transition-matrix elements for the 2p −1 t 1 2g core-excited states as smaller than for 2p −1 e 1 g . Neglecting the dominant (> 99%) nonradiative decay channels of the core-excited states, they postulate an unquantified longer lifetime of the 2p −1 t 1 2g over the 2p −1 e 1 g states. With these assumptions they invoke a more "pronounced" or more "complete" electron delocalization in the 2p −1 t 1 2g over the 2p −1 e 1 g resonances that should be visible as state depend-fluorescence yields depending on the orbital population of t 2g and e g states.The claims by Bokarev et al. are not sufficiently supported. First, the correlation between 2p excitations into t 2g orbitals and the appearance of spectral differences is not substantiated. Bokarev et al. display dominant t 2g occupations for Fe 3þ in Fig. 1(b) at 709.9, 710.4, and 710.7 eV and for ½FeClðH 2 OÞ 5 2þ and ½FeCl 2 ðH 2 OÞ 4 þ above 709 eV but the spectral distortions are minor or not present at these energies. In tu...

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Intrinsic deviations in fluorescence yield detected x-ray absorption spectroscopy: the case of the transition metal L_2,3edges

Cited by 52 publications

References 37 publications

Viewing the Valence Electronic Structure of Ferric and Ferrous Hexacyanide in Solution from the Fe and Cyanide Perspectives

Viewing the Valence Electronic Structure of Ferric and Ferrous Hexacyanide in Solution from the Fe and Cyanide Perspectives

State-dependent fluorescence yields through the core-valence Coulomb exchange parameter

Comment on “State-Dependent Electron Delocalization Dynamics at the Solute-Solvent Interface: Soft-X-ray Absorption Spectroscopy and Ab Initio Calculations”

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Intrinsic deviations in fluorescence yield detected x-ray absorption spectroscopy: the case of the transition metal L2,3edges

Cited by 52 publications

References 37 publications

Viewing the Valence Electronic Structure of Ferric and Ferrous Hexacyanide in Solution from the Fe and Cyanide Perspectives

Viewing the Valence Electronic Structure of Ferric and Ferrous Hexacyanide in Solution from the Fe and Cyanide Perspectives

State-dependent fluorescence yields through the core-valence Coulomb exchange parameter

Comment on “State-Dependent Electron Delocalization Dynamics at the Solute-Solvent Interface: Soft-X-ray Absorption Spectroscopy and Ab Initio Calculations”

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Intrinsic deviations in fluorescence yield detected x-ray absorption spectroscopy: the case of the transition metal L_2,3edges