Solvation and speciation of cobalt(II). A theoretical X-ray absorption and RIXS study

Basmah H. Allehyani; Walid I. Hassan; Saadullah G. Aziz; Rifaat H. Hilal; Oliver Kühn; Sergey I. Bokarev

doi:10.1016/j.chemphys.2020.110681

Solvation and speciation of cobalt(II). A theoretical X-ray absorption and RIXS study

Basmah H. Allehyani, Walid I. Hassan, Saadullah G. Aziz, Rifaat H. Hilal, Oliver Kühn, Sergey I. Bokarev

Research output: Contribution to journal › Article › peer-review

6 Scopus citations

Abstract

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−xCl_x]^(2−x)+, and tetrahedral, [Co(H₂O)_4−xCl_x]^(2−x)+, coordination. X-ray absorption spectra show distinct differences in the L₃ band only. Here, the best agreement between theory and experiment is obtained for the hexaaqua complex [Co(H₂O)₆]²⁺. For better identification of particular species it is proposed to use RIXS spectroscopy, which shows pronounced species-dependent inelastic features.

Original language	English
Article number	110681
Journal	Chemical Physics
Volume	532
DOIs	https://doi.org/10.1016/j.chemphys.2020.110681
State	Published - 1 Apr 2020
Externally published	Yes

Keywords

Ab initio theory
Metal ions
Solvation
X-ray spectroscopy

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10.1016/j.chemphys.2020.110681

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title = "Solvation and speciation of cobalt(II). A theoretical X-ray absorption and RIXS study",

abstract = "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 between theory and experiment is obtained for the hexaaqua complex [Co(H2O)6]2+. For better identification of particular species it is proposed to use RIXS spectroscopy, which shows pronounced species-dependent inelastic features.",

keywords = "Ab initio theory, Metal ions, Solvation, X-ray spectroscopy",

author = "Allehyani, {Basmah H.} and Hassan, {Walid I.} and Aziz, {Saadullah G.} and Hilal, {Rifaat H.} and Oliver K{\"u}hn and Bokarev, {Sergey I.}",

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year = "2020",

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doi = "10.1016/j.chemphys.2020.110681",

language = "English",

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T1 - Solvation and speciation of cobalt(II). A theoretical X-ray absorption and RIXS study

AU - Allehyani, Basmah H.

AU - Hassan, Walid I.

AU - Aziz, Saadullah G.

AU - Hilal, Rifaat H.

AU - Kühn, Oliver

AU - Bokarev, Sergey I.

PY - 2020/4/1

Y1 - 2020/4/1

N2 - 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 between theory and experiment is obtained for the hexaaqua complex [Co(H2O)6]2+. For better identification of particular species it is proposed to use RIXS spectroscopy, which shows pronounced species-dependent inelastic features.

AB - 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 between theory and experiment is obtained for the hexaaqua complex [Co(H2O)6]2+. For better identification of particular species it is proposed to use RIXS spectroscopy, which shows pronounced species-dependent inelastic features.

KW - Ab initio theory

KW - Metal ions

KW - Solvation

KW - X-ray spectroscopy

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U2 - 10.1016/j.chemphys.2020.110681

DO - 10.1016/j.chemphys.2020.110681

M3 - Article

AN - SCOPUS:85078735247

SN - 0301-0104

VL - 532

JO - Chemical Physics

JF - Chemical Physics

M1 - 110681

ER -

Solvation and speciation of cobalt(II). A theoretical X-ray absorption and RIXS study

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Keywords

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