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  DFT Studies and Experiments on Biocatalytic Centers: Structure, Vibrations, and Core Excitations of the K[VO(O2)Hheida] Complex

Sun, L., Hermann, K., Noack, J., Timpe, O., Teschner, D., Hävecker, M., et al. (2014). DFT Studies and Experiments on Biocatalytic Centers: Structure, Vibrations, and Core Excitations of the K[VO(O2)Hheida] Complex. The Journal of Physical Chemistry C, 118(42), 24611-24622. doi:10.1021/jp5081719.

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Sun, Lili1, Author           
Hermann, Klaus1, Author           
Noack, Johannes1, Author           
Timpe, Olaf1, Author           
Teschner, Detre1, Author           
Hävecker, Michael1, 2, Author           
Trunschke, Annette1, Author           
Schlögl, Robert1, Author           
Affiliations:
1Inorganic Chemistry, Fritz Haber Institute, Max Planck Society, ou_24023              
2Helmholtz-Zentrum Berlin fuer Materialien und Energy GmbH, Division Solar Energy Research, Elektronenspeicherring BESSY II, ou_persistent22              

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 Abstract: Geometric and electronic properties of the K[VO(O2)Hheida] complex, which serves as a functional model for vanadium haloperoxidase enzymes, as well as of the molecular ions (VO(O2)Hheida) and (VO(O)Hheida) are evaluated using density-functional theory (DFT). Theoretical results of equilibrium structures, vibrational excitations, oxygen 1s core ionization and excitation are compared with measured data. The theoretical equilibrium structure of the K[VO(O2)Hheida] complex agrees quite well with the corresponding molecular structure in crystalline K[VO(O2)Hheida]·2(H2O) and differs only a little from that of the (VO(O2)Hheida) ion. The potassium appears in the K[VO(O2)Hheida] complex as a positive K+ species binding only electrostatically with no orbital hybridization to the (VO(O2)Hheida) part, which is also obvious from the respective orbital analyses and densities-of-states. The vibrational modes of peroxo and vanadyl oxygen in K[VO(O2)Hheida] are strongly coupled, and the calculated excitation energies can explain details of the experimental infrared and Raman spectra. The theoretical O 1s core ionization potentials (IP) vary between the different oxygen species and are consistent with results from X-ray photoemission (XPS). Theoretical O 1s core excitation spectra are confirmed by results from O K-edge NEXAFS measurements for crystalline K[VO(O2)Hheida]·2(H2O) under oxygen and helium pressure. The difference between the two experimental spectra can be explained by the presence of oxygen-deficient species based on the theoretical findings for the (VO(O)Hheida)− species.

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Language(s): eng - English
 Dates: 2014-09-242014-08-122014-09-262014-09-262014-10-23
 Publication Status: Published in print
 Pages: 12
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jp5081719
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Title: The Journal of Physical Chemistry C
  Other : J. Phys. Chem. C
Source Genre: Journal
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Publ. Info: Washington DC : American Chemical Society
Pages: - Volume / Issue: 118 (42) Sequence Number: - Start / End Page: 24611 - 24622 Identifier: ISSN: 1932-7447
CoNE: https://pure.mpg.de/cone/journals/resource/954926947766