On the Accuracy of Calculated Reduction Potentials of Selected Group 8 (Fe, Ru, and Os) Octahedral Complexes

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F13%3A00396344" target="_blank" >RIV/61388963:_____/13:00396344 - isvavai.cz</a>
Result on the web
<a href="http://dx.doi.org/10.1021/jp406772u" target="_blank" >http://dx.doi.org/10.1021/jp406772u</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/jp406772u" target="_blank" >10.1021/jp406772u</a>

Result language
angličtina
Original language name
On the Accuracy of Calculated Reduction Potentials of Selected Group 8 (Fe, Ru, and Os) Octahedral Complexes
Original language description
The theoretical calculations of reduction potentials for the [M(H2O)(6)](2+/3+), [M(NH3)(6)](2+/3+), [M(en)(3)](2+/3+), [M(bipy)(3)](2+/3+), [M(CN)(6)](4-/3-), and [MCl6](4-/3-) systems (M = Fe, Os, Ru) were carried out. The DFT(PBE)/def2-TZVP//DFT(PBE)/def2-SVP quantum chemical method was employed to obtain presumably accurate ionization energies, whereas the conductor-like screening model for real solvents (COSMO-RS) was selected as the most suitable method for calculations of solvation energies of the oxidized and reduced forms of the studied species. It has been shown that COSMO-RS may overcome problems related to directionality of hydrogen bonds in the second solvation sphere that previously led to errors of similar to 1 V for the [Ru(H2O)(6)](2+)complex employing PCM-like models. Thus, most of the values for (2+) -> (3+) oxidations are now within 0.1-0.2 V from the experimental data, once the anticipated spin-orbit coupling effects in Os complexes (downshifting the calculated re
Czech name
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Czech description
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Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CF - Physical chemistry and theoretical chemistry
OECD FORD branch
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Project
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Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year
2013
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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