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Viewing the Valence Electronic Structure of Ferric and Ferrous Hexacyanide in Solution from the Fe and Cyanide Perspectives
Helmholtz Zentrum Berlin Mat & Energie GmbH, Inst Methods & Instrumentat Synchrotron Radiat Re, Albert Einstein Str 15, D-12489 Berlin, Germany.;Univ Potsdam, Inst Phys & Astron, Karl Liebknecht Str 24-25, D-14476 Potsdam, Germany.;SLAC Natl Accelerator Lab, PULSE Inst, Menlo Pk, CA 94025 USA..
SLAC Natl Accelerator Lab, PULSE Inst, Menlo Pk, CA 94025 USA.;Beijing Normal Univ, Dept Phys, Beijing 100875, Peoples R China..
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.
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2016 (English)In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 120, no 29, 7182-7194 p.Article in journal (Refereed) Published
Abstract [en]

The valence-excited states of ferric and ferrous hexacyanide ions in aqueous solution were mapped by resonant inelastic X-ray scattering (RIXS) at the Fe L-2,L-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 ligand-to-metal and metal-to-ligand charge-transfer excited states. Ab initio calculations utilizing the RASPT2 method were used to simulate the Fe L-2,L-3-edge RIXS spectra and enabled quantification of the covalencies of both occupied and empty orbitals of pi and sigma symmetry. We found that pi back-donation in the ferric complex is smaller than that in the ferrous complex. This is evidenced by the relative amounts of Fe 3d character in the nominally 2 pi CN- molecular orbital of 7% and 9% in ferric and ferrous hexacyanide, respectively. Utilizing the direct sensitivity of Fe L-3-edge RIXS to the Fe 3d character in the occupied molecular orbitals, we also found that the donation interactions are dominated by sigma bonding. The latter was found to be stronger in the ferric complex, with an Fe 3d contribution to the nominally 5 sigma 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.

Place, publisher, year, edition, pages
2016. Vol. 120, no 29, 7182-7194 p.
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-304444DOI: 10.1021/acs.jpcb.6b04751ISI: 000380730300016PubMedID: 27380541OAI: oai:DiVA.org:uu-304444DiVA: diva2:1033041
Funder
Swedish Research CouncilCarl Tryggers foundation Knut and Alice Wallenberg Foundation, KAW-2013.0020
Available from: 2016-10-05 Created: 2016-10-05 Last updated: 2017-11-30Bibliographically approved

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