Solvation and Speciation of Cobalt(II). A Theoretical X-Ray Absorption and RIXS Study

The X-ray spectroscopic signatures of solvated Co2+ ions mimicking the aqueous solution of CoCl2 are investigated accounting for multiconfigurational as well as spin-orbit coupling effects. To this end the RASSCF/RASSI methodology with second order corrections due to dynamical correlation (RASPT2) is employed. Emphasis is put on the identification of spectral signatures of different species in octahedral, [Co(H2O)6-xClx](2-x)+, and tetrahedral, [Co(H2O)4-xClx](2-x)+,coordination. X-ray absorption spectra show distinct differences in the L3 band only. Here, the best agreement is obtained for the hexa-aqua complex [Co(H2O)6]2+. For better identification it is proposed to use RIXS spectroscopy, which shows pronounced species-dependent inelastic features.

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Solvation and Speciation of Cobalt(II). A Theoretical X-Ray Absorption and RIXS Study

10.26434/chemrxiv.11378643.v2 ◽

2020 ◽

Author(s):

Basmah H. Allehyani ◽

Walid I. Hassan ◽

Saadullah Aziz ◽

Rifaat H. Hilal ◽

Oliver Kühn ◽

...

Keyword(s):

Aqueous Solution ◽

Absorption Spectra ◽

Aqua Complex ◽

Spin Orbit Coupling ◽

Spin Orbit ◽

Dynamical Correlation ◽

X Ray ◽

Spectral Signatures ◽

Spectroscopic Signatures ◽

X Ray Absorption

The X-ray spectroscopic signatures of solvated Co2+ ions mimicking the aqueous solution of CoCl2 are investigated accounting for multiconfigurational as well as spin-orbit coupling effects. To this end the RASSCF/RASSI methodology with second order corrections due to dynamical correlation (RASPT2) is employed. Emphasis is put on the identification of spectral signatures of different species in octahedral, [Co(H2O)6-xClx](2-x)+, and tetrahedral, [Co(H2O)4-xClx](2-x)+,coordination. X-ray absorption spectra show distinct differences in the L3 band only. Here, the best agreement is obtained for the hexa-aqua complex [Co(H2O)6]2+. For better identification it is proposed to use RIXS spectroscopy, which shows pronounced species-dependent inelastic features.

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Systematics of the Relation between Spin-Orbit Splitting in the Valence Band and the Branching Ratio in X-Ray Absorption Spectra

EPL (Europhysics Letters) ◽

10.1209/0295-5075/4/9/022 ◽

1987 ◽

Vol 4 (9) ◽

pp. 1083-1086 ◽

Cited By ~ 24

Author(s):

B. T Thole ◽

G. van der Laan

Keyword(s):

Valence Band ◽

Absorption Spectra ◽

Branching Ratio ◽

Spin Orbit ◽

Orbit Splitting ◽

X Ray ◽

Spin Orbit Splitting ◽

X Ray Absorption

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On the origin of dips in total fluorescence yield X-ray absorption spectra: Partial and inverse partial fluorescence yield at the L-edge of cobalt aqueous solution

Chemical Physics Letters ◽

10.1016/j.cplett.2012.07.067 ◽

2012 ◽

Vol 546 ◽

pp. 164-167 ◽

Cited By ~ 23

Author(s):

Mikhail A. Soldatov ◽

Kathrin M. Lange ◽

Malte D. Gotz ◽

Nicholas Engel ◽

Ronny Golnak ◽

...

Keyword(s):

Aqueous Solution ◽

Absorption Spectra ◽

Fluorescence Yield ◽

X Ray ◽

Total Fluorescence ◽

X Ray Absorption

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A combined DFT and restricted open-shell configuration interaction method including spin-orbit coupling: Application to transition metal L-edge X-ray absorption spectroscopy

The Journal of Chemical Physics ◽

10.1063/1.4804607 ◽

2013 ◽

Vol 138 (20) ◽

pp. 204101 ◽

Cited By ~ 145

Author(s):

Michael Roemelt ◽

Dimitrios Maganas ◽

Serena DeBeer ◽

Frank Neese

Keyword(s):

Transition Metal ◽

Absorption Spectroscopy ◽

Configuration Interaction ◽

Open Shell ◽

Spin Orbit Coupling ◽

Spin Orbit ◽

Interaction Method ◽

Configuration Interaction Method ◽

X Ray ◽

X Ray Absorption

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Darstellung und spektroskopische Charakterisierung von Tetrachloro- und Tetrabromo-Oxalatoiridaten(IV) / Preparation and Spectroscopical Characterization of Tetrachloro- and Tetrabromoiridates(IV)

Zeitschrift für Naturforschung B ◽

10.1515/znb-1982-1213 ◽

1982 ◽

Vol 37 (12) ◽

pp. 1553-1557 ◽

Cited By ~ 2

Author(s):

H. Schulz ◽

W. Preetz

Keyword(s):

Aqueous Solution ◽

Fine Structure ◽

Absorption Spectra ◽

Raman Spectra ◽

Point Group ◽

Vibration Modes ◽

Spin Orbit Coupling ◽

Spin Orbit ◽

Ir And Raman

On treatment of [IrX6]2- with oxalate in aqueous solution at first [IrX4OX]3- (X = Cl, Br) is formed, which after extraction with pentylammonium ions into CH2Cl2 can be oxidised by X2 to give the corresponding pure Ir(IV) complexes [IrX4OX]2-. The IR and Raman spectra are assigned according to point group C2V- The UV/VIS absorption spectra show strong CT bands of transitions from "(π + σ)tlu"- and "πt2U"-ligand niveaus to t2g5 (IrIV). These are split into three components by spin-orbit coupling and corresponding to the different groups of ligands: Xtr2, Xc2, ox. The spectrum of (TBA)2[IrBr4OX] recorded at 10 K is highly resolved, showing a splitting of the Brtr2 → Ir(IV) and Bc2 → Ir(IV) transitions by 1000-1400 cm-1. In the NIR-region two d-d-transitions are observed superimposed with a fine structure by coupling with vibration modes

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