Chemical bonding in aqueous ferrocyanide: Experimental and theoretical X-ray spectroscopic study

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

doi:10.1021/jp411782y

Chemical bonding in aqueous ferrocyanide: Experimental and theoretical X-ray spectroscopic study

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

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58 Scopus citations

Abstract

Resonant inelastic X-ray scattering (RIXS) and X-ray absorption (XA) experiments at the iron L- and nitrogen K-edge are combined with high-level first-principles restricted active space self-consistent field (RASSCF) calculations for a systematic investigation of the nature of the chemical bond in potassium ferrocyanide in aqueous solution. The atom- and site-specific RIXS excitations allow for direct observation of ligand-to-metal (Fe L-edge) and metal-to-ligand (N K-edge) charge-transfer bands and thereby evidence for strong σ-donation and π-backdonation. The effects are identified by comparing experimental and simulated spectra related to both the unoccupied and occupied molecular orbitals in solution.

Original language	English
Pages (from-to)	1555-1563
Number of pages	9
Journal	Journal of Physical Chemistry B
Volume	118
Issue number	6
DOIs	https://doi.org/10.1021/jp411782y
State	Published - 13 Feb 2014
Externally published	Yes

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title = "Chemical bonding in aqueous ferrocyanide: Experimental and theoretical X-ray spectroscopic study",

abstract = "Resonant inelastic X-ray scattering (RIXS) and X-ray absorption (XA) experiments at the iron L- and nitrogen K-edge are combined with high-level first-principles restricted active space self-consistent field (RASSCF) calculations for a systematic investigation of the nature of the chemical bond in potassium ferrocyanide in aqueous solution. The atom- and site-specific RIXS excitations allow for direct observation of ligand-to-metal (Fe L-edge) and metal-to-ligand (N K-edge) charge-transfer bands and thereby evidence for strong σ-donation and π-backdonation. The effects are identified by comparing experimental and simulated spectra related to both the unoccupied and occupied molecular orbitals in solution.",

author = "Nicholas Engel and Bokarev, {Sergey I.} and Edlira Suljoti and Raul Garcia-Diez and Lange, {Kathrin M.} and Kaan Atak and Ronny Golnak and Alexander Kothe and Marcus Dantz and Oliver K{\"u}hn and Aziz, {Emad F.}",

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doi = "10.1021/jp411782y",

language = "English",

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TY - JOUR

T1 - Chemical bonding in aqueous ferrocyanide

T2 - Experimental and theoretical X-ray spectroscopic study

AU - Engel, Nicholas

AU - Bokarev, Sergey I.

AU - Suljoti, Edlira

AU - Garcia-Diez, Raul

AU - Lange, Kathrin M.

AU - Atak, Kaan

AU - Golnak, Ronny

AU - Kothe, Alexander

AU - Dantz, Marcus

AU - Kühn, Oliver

AU - Aziz, Emad F.

PY - 2014/2/13

Y1 - 2014/2/13

N2 - Resonant inelastic X-ray scattering (RIXS) and X-ray absorption (XA) experiments at the iron L- and nitrogen K-edge are combined with high-level first-principles restricted active space self-consistent field (RASSCF) calculations for a systematic investigation of the nature of the chemical bond in potassium ferrocyanide in aqueous solution. The atom- and site-specific RIXS excitations allow for direct observation of ligand-to-metal (Fe L-edge) and metal-to-ligand (N K-edge) charge-transfer bands and thereby evidence for strong σ-donation and π-backdonation. The effects are identified by comparing experimental and simulated spectra related to both the unoccupied and occupied molecular orbitals in solution.

AB - Resonant inelastic X-ray scattering (RIXS) and X-ray absorption (XA) experiments at the iron L- and nitrogen K-edge are combined with high-level first-principles restricted active space self-consistent field (RASSCF) calculations for a systematic investigation of the nature of the chemical bond in potassium ferrocyanide in aqueous solution. The atom- and site-specific RIXS excitations allow for direct observation of ligand-to-metal (Fe L-edge) and metal-to-ligand (N K-edge) charge-transfer bands and thereby evidence for strong σ-donation and π-backdonation. The effects are identified by comparing experimental and simulated spectra related to both the unoccupied and occupied molecular orbitals in solution.

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JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

IS - 6

ER -

Chemical bonding in aqueous ferrocyanide: Experimental and theoretical X-ray spectroscopic study

Abstract

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