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

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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

Název v anglickém jazyce

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

Popis výsledku anglicky

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

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

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Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2013

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Physical Chemistry C

ISSN

1932-7447

e-ISSN

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Svazek periodika

117

Číslo periodika v rámci svazku

33

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

7

Strana od-do

16871-16877

Kód UT WoS článku

000323593100014

EID výsledku v databázi Scopus

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