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  Comparative X-Ray Absorption Analysis of the Spectrum of Vacant Electronic States in Cobalt and Nickel Tetraphenylporphyrin Complexes

Svirskiy, G. I., Generalov, A. V., Klyushin, A., Simonov, K. A., Krasnikov, S. A., Vinogradov, N. A., et al. (2018). Comparative X-Ray Absorption Analysis of the Spectrum of Vacant Electronic States in Cobalt and Nickel Tetraphenylporphyrin Complexes. Physics of the Solid State, 60(3), 581-591. doi:10.1134/S1063783418030307.

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Item Permalink: http://hdl.handle.net/21.11116/0000-0001-1B4F-A Version Permalink: http://hdl.handle.net/21.11116/0000-0001-3E42-0
Genre: Journal Article

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2018
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Pleiades Publ.
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 Creators:
Svirskiy, G. I.1, Author
Generalov, A. V.1, 2, Author
Klyushin, Alexander1, 3, 4, Author              
Simonov, K. A.1, 2, 5, Author
Krasnikov, S. A.1, 6, Author
Vinogradov, N. A.1, 2, Author
Trigub, A. L.7, Author
Zubavichus, Ya. V.7, Author
Preobrazhenski, A. B.1, 2, Author
Vinogradov, A. S.1, Author
Affiliations:
1Saint Petersburg State University, St. Petersburg, 199034 Russia, escidoc:persistent22              
2MAX IV Laboratory, University of Lund, PO Box 118, Lund, Sweden, escidoc:persistent22              
3Inorganic Chemistry, Fritz Haber Institute, Max Planck Society, escidoc:24023              
4Research Group Catalysis for Energy, Helmholtz Zentrum Berlin, Berlin, Germany, escidoc:persistent22              
5Department of Physics and Astronomy, Uppsala University, Box 516, Uppsala, Sweden, escidoc:persistent22              
6School of Physical Sciences, Dublin City University, Glasnevin, Dublin 9, Republic of Ireland, escidoc:persistent22              
7National Research Center “Kurchatov Institute”, Moscow, 123182 Russia, escidoc:persistent22              

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 Abstract: 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 eg MOs due to the exchange interaction between 3d electrons in partially filled 3db2g and 3db1g or 3deg MOs. The spectrum of vacant states in CoTPP differs from that in NiTPP also due to the smaller energy distance between 3db1g and eg MOs and the different positions of nonbonding MOs with the C2p character of the porphine ligand.

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Language(s): eng - English
 Dates: 2017-07-032018-03-162018-03
 Publication Status: Published in print
 Pages: 11
 Publishing info: -
 Table of Contents: -
 Rev. Method: Peer
 Identifiers: DOI: 10.1134/S1063783418030307
 Degree: -

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Title: Physics of the Solid State
Source Genre: Journal
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Publ. Info: Pleiades Publ.
Pages: 11 Volume / Issue: 60 (3) Sequence Number: - Start / End Page: 581 - 591 Identifier: ISSN: 1063-7834
CoNE: http://pubman.mpdl.mpg.de/cone/journals/resource/991042724222234