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Comparative X-Ray Absorption Analysis of the Spectrum of Vacant Electronic States in Cobalt and Nickel Tetraphenylporphyrin Complexes
St Petersburg State Univ, St Petersburg, Russia.
St Petersburg State Univ, St Petersburg , Russia; Lund Univ, MAX Lab 4, Lund, Sweden.
St Petersburg State Univ, St Petersburg, Russia; Helmholtz Zentrum Berlin, Res Grp Catalysis Energy, Berlin, Germany; Max Planck Gesell, Dept Inorgan Chem, Fritz Haber Inst, Berlin, Germany.
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and Condensed Matter Physics. St Petersburg State Univ, St Petersburg, Russia; Lund Univ, MAX Lab 4, Lund, Sweden.
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2018 (English)In: Physics of the solid state, ISSN 1063-7834, E-ISSN 1090-6460, Vol. 60, no 3, p. 581-591Article in journal (Refereed) Published
Abstract [en]

The energy distributions and the properties of the lower vacant electronic states in cobalt and nickel tetraphenylporphyrin complexes CoTPP and NiTPP are studied by X-ray absorption spectroscopy. Quasimolecular analysis of the experimental absorption spectra measured in the region of the 2p and 1s ionization thresholds of complexing metal atoms, as well as the 1s thresholds of ligand atoms (nitrogen and carbon), is based on the comparison of the corresponding spectra with each other and with the spectra of the simplest nickel porphyrin NiP. It has been established that, despite a general similarity of the spectra of nitrogen and carbon in CoTPP and NiTPP, the fine structure of the 2p and 1s absorption spectra of cobalt and nickel atoms are radically different. The observed differences in the spectra of cobalt and nickel are associated with the features of the energy distribution of vacant 3d electron states. The presence in CoTPP of the partially filled valence 3db2g molecular orbital (MO) results in the appearance in the cobalt spectra of a low-energy band, which is absent in the spectrum of nickel in NiTPP and leads to a doublet structure of transitions to b1g and e g MOs due to the exchange interaction between 3d electrons in partially filled 3db2g and 3db1g or 3de g MOs. The spectrum of vacant states in CoTPP differs from that in NiTPP also due to the smaller energy distance between 3db1g and e g MOs and the different positions of nonbonding MOs with the C2p character of the porphine ligand.

Place, publisher, year, edition, pages
2018. Vol. 60, no 3, p. 581-591
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Condensed Matter Physics
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URN: urn:nbn:se:uu:diva-350880DOI: 10.1134/S1063783418030307ISI: 000427598800027OAI: oai:DiVA.org:uu-350880DiVA, id: diva2:1209420
Available from: 2018-05-23 Created: 2018-05-23 Last updated: 2018-05-25Bibliographically approved

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Simonov, Konstantin

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