Chemical Bonding in Aqueous Ferrocyanide: Experimental and Theoretical X-ray Spectroscopic Study

Engel, Nicholas; Bokarev, Sergey I.; Suljoti, Edlira; Garcia-Diez, Raul; Lange, Kathrin M.; Atak, Kaan; Golnak, Ronny; Kothe, Alexander; Dantz, Marcus; Kühn, Oliver; Aziz, Emad F.

doi:10.1021/jp411782y

Cited by 62 publications

(110 citation statements)

References 44 publications

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“…16 The DFT and Valence Bond Configuration Interaction (VBCI) results from Hocking et al 17 and Lundberg et al 18 show π-back-donation to be larger by approximately a factor of 2 compared to the RASPT2 results presented here. Additionally, no considerable difference in π-back-donation between ferri-and ferrocyanide was found.…”

Section: Discussionmentioning

confidence: 48%

“…16 Here we aim to refine, complement and extend these results both in terms of new experiments and new calculations by additionally addressing ferricyanide and by comparing both compounds in detail. Furthermore we recorded the full RIXS planes (in contrast to a limited number of XES or RIXS spectra at selected incident photon energies) both at the Fe L2,3 and the N K-edges.…”

Section: Introductionmentioning

confidence: 93%

“…17 Our RASPT2 and CTM calculations for the Fe L3-edge are displayed in where the intensity ratio of the bM and cM resonances is not well reproduced and the energy splitting is overestimated by about 2 eV. 16 This is primarily due to the limited flexibility in the active space and differences in orbital optimization. Additionally, in the present calculations we found that inclusion of the dynamical correlation reduces the energy difference between the bM and cM resonances and increases the relative intensity of the cM resonance.…”

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

confidence: 98%

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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: Discussionmentioning

confidence: 48%

Section: Introductionmentioning

confidence: 93%

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

confidence: 98%

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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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“…This can also be seen from the numerous reported experimental investigations of hexacyanoferrates in the past. [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] According to the literature hexacyanoferrate(II) ions, [Fe(CN) 6 ] 4− , are octahedral coordination complexes, which, depending on pH and cyanide concentration, tend to dissociate upon heat or light exposure 14,15,19,31 or in presence of mercury(II), 28 silver(I), 24,28 palladium(II) 28 and gold(III) 28 as they form even stronger complexes with cyanide than iron(II) and iron(III). A degradation of hexacyanoferrates by microorganisms has also been reported.…”

Section: Introductionmentioning

confidence: 99%

Is the Hexacyanoferrate(II) Anion Stable in Aqueous Solution? A Combined Theoretical and Experimental Study

et al. 2015

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A combined theoretical and experimental study has been performed to elucidate the structural and dynamical properties of aqueous hexacyanoferrate(II) isolated and in presence of potassium ions. It is shown that in absence of counter ions, the highly negatively charged hexacyanoferrate(II) complex is not stable in aqueous solution.However, if the high negative charge is compensated by potassium counter ions, a stable complex is observed, which is proven by theoretical simulations as well as by EXAFS experiments. From the simulation it is found that potassium ions surrounding the complex are highly mobile and thus, cannot be observed in the experiment. The structure of aqueous hexacyanoferrate(II) in presence of potassium ions is identical to that of the solid state structure, but the mobility of potassium ions is significantly increased in the liquid. These highly mobile potassium ions circulating the complex should be the reason for the very short hydrogen bond lifetimes in the femtosecond range of the cyanide ligands.

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“…We address the application of the X-ray metal L-edge and ligand Kedge spectroscopy to unraveling electronic structure, nature of chemical bonds, oxidation, and spin-states, the interplay of radiative and non-radiative decay channels in transition metal complexes. The investigated systems range from the small prototypical coordination compounds [4][5][6] and catalysts [7] to the aggregates of biomolecules [8]. …”

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confidence: 99%

Soft X-ray spectroscopy of transition metal compounds: a theoretical perspective

et al. 2016

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Abstract.To date, X-ray spectroscopy has become a routine tool that can reveal highly local and element-specific information on the electronic structure of atoms in complex environments. Here, we report on the development of an efficient and versatile theoretical methodology for the treatment of soft X-ray spectra of transition metal compounds based on the multi-configurational self-consistent field electronic structure theory. A special focus is put on the L-edge photon-in/photon-out and photonin/electron-out processes, i.e. X-ray absorption, resonant inelastic scattering, partial fluorescence yield, and photoelectron spectroscopy, all treated on the same theoretical footing. The investigated systems range from small prototypical coordination compounds and catalysts to aggregates of biomolecules.Tracing atomic and molecular levels in the course of various physical and chemical processes, X-ray spectroscopy is one of the most powerful tools to access structure and properties of matter in different states of aggregation. X-ray spectroscopic techniques probe the local electronic structure of a particular atom in its environment. This is in contrast to UV/vis spectroscopy, where transitions generally occur between delocalized molecular orbitals. The combination of different absorption, emission (scattering) as well as photo-and autoionization X-ray methods allows addressing various aspects of ultrafast dynamics and identification of short-lived intermediates of catalytic reactions. However, interpretation of complex experimental spectra and verification of experimental hypotheses is a non-trivial task and a powerful first principles theoretical approach that allows for a systematic investigation of a broad class of compounds is needed. An additional complexity stems from strong electron correlation and spin-orbit coupling in the core-excited electronic states.We aim at the development of an efficient and versatile theoretical methodology for the treatment of soft X-ray spectra of transition metal compounds based on the multiconfigurational self-consistent field electronic structure theory combined with a perturbative LS-coupling scheme for spin-orbit coupling [1]. A special focus is put on the L-edge photonin/photon-out and photon-in/electron-out processes, i.e. X-ray absorption, resonant inelastic scattering, partial fluorescence yield, and photoelectron spectroscopy treated on the same theoretical footing [2,3]. We address the application of the X-ray metal L-edge and ligand Kedge spectroscopy to unraveling electronic structure, nature of chemical bonds, oxidation,

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Chemical Bonding in Aqueous Ferrocyanide: Experimental and Theoretical X-ray Spectroscopic Study

Cited by 62 publications

References 44 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

Is the Hexacyanoferrate(II) Anion Stable in Aqueous Solution? A Combined Theoretical and Experimental Study

Soft X-ray spectroscopy of transition metal compounds: a theoretical perspective

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