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  The vibrational spectrum of FeO2+ isomers - Theoretical benchmark and experiment

Maier, T. M., Boese, A. D., Sauer, J., Wende, T., Fagiani, M. R., & Asmis, K. R. (2014). The vibrational spectrum of FeO2+ isomers - Theoretical benchmark and experiment. The Journal of Chemical Physics, 140(20): 204315. doi:10.1063/1.4878667.

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 Creators:
Maier, Toni M.1, Author
Boese, A. Daniel1, Author
Sauer, Joachim1, Author
Wende, Torsten2, Author              
Fagiani, Matias Ruben2, Author              
Asmis, Knut R.2, 3, Author              
Affiliations:
1Institut für Chemie, Humboldt-Universität zu Berlin, Unter den Linden 6, D 10099 Berlin, Germany , ou_persistent22              
2Molecular Physics, Fritz Haber Institute, Max Planck Society, ou_634545              
3Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Linnéstrasse 2, D-04103 Leipzig, Germany , ou_persistent22              

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Free keywords: Density functional theory Iron Oxidation Electron correlation calculations Infrared spectra
 Abstract: Infrared photodissociation is used to record the vibrational spectrum of FeO2+(He)2-4 which shows three bands at 1035, 980, and 506 cm-1. Quantum chemical multi-reference configuration interaction calculations (MRCISD) of structures and harmonic frequencies show that these bands are due to two different isomers, an inserted dioxo complex with Fe in the +V oxidation state and a side-on superoxo complex with Fe in the +II oxidation state. These two are separated by a substantial barrier, 53 kJ/mol, whereas the third isomer, an end-on complex between Fe+ and an O2 molecule, is easily converted into the side-on complex. For all three isomers, states of different spin multiplicity have been considered. Our best energies are computed at the MRCISD+Q level, including corrections for complete active space and basis set extension, core-valence correlation, relativistic effects, and zero-point vibrational energy. The average coupled pair functional (ACPF) yields very similar energies. Density functional theory (DFT) differs significantly from our best estimates for this system, with the TPSS functional yielding the best results. The other functionals tested are BP86, PBE, B3LYP, TPSSh, and B2PLYP. Complete active space second order perturbation theory (CASPT2) performs better than DFT, but less good than ACPF

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Language(s): eng - English
 Dates: 2014-03-122014-05-072014-05-282014-05-28
 Publication Status: Published in print
 Pages: 12
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1063/1.4878667
 Degree: -

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Title: The Journal of Chemical Physics
  Other : J. Chem. Phys.
Source Genre: Journal
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Publ. Info: Woodbury, N.Y. : American Institute of Physics
Pages: - Volume / Issue: 140 (20) Sequence Number: 204315 Start / End Page: - Identifier: ISSN: 0021-9606
CoNE: https://pure.mpg.de/cone/journals/resource/954922836226