To calculate the redox potential it would be better to consider the thermodynamical parameters like free energy or enthalpy. You need to optimize the molecule and at the same time do frequency calculations and that basically yields the thermodynamical parameters. u can refer this paper of Frank Neese Inorg. Chem. 2011, 50, 12064.

To calculate the redox potential it would be better to consider the thermodynamical parameters like free energy or enthalpy. You need to optimize the molecule and at the same time do frequency calculations and that basically yields the thermodynamical parameters. u can refer this paper of Frank Neese Inorg. Chem. 2011, 50, 12064.

Thank you for your answer, Subrata and Malte. All the best!

Francesca

I also suggest the following work in which the authors reduce errors from the choice of method by using a reference redox couple and achieve a standard deviation of 64 mV:

Konezny, Steven J., Mark D. Doherty, Oana R. Luca, Robert H. Crabtree, Grigorii L. Soloveichik, e Victor S. Batista. “Reduction of Systematic Uncertainty in DFT Redox Potentials of Transition-Metal Complexes”. The Journal of Physical Chemistry C 116, nº 10 (march 15, 2012): 6349–6356. doi:10.1021/jp300485t.

http://dx.doi.org/10.1021/jp300485t

Thanks Daniel! I am very interested in transition metals systems!

See the attachment.

Thanks Mohammad, really useful!

You might want to check the work of Sprik et al. Here are some references:

J. AM. CHEM. SOC. 2004 , 126 , 3928 -3938

Phs. Rev. Lett. 2002, 88, 213002

Dear Francesca Rondinelli,

Here are some references that might help you.

(1) Davis, A. P.; Fry, A. J. Experimental and Computed Absolute Redox Potentials of Polycyclic Aromatic Hydrocarbons are Highly Linearly Correlated Over a Wide Range of Structures and Potentials. J. Phys. Chem. A 2010, 114, 12299-12304.

(2) Han, Y.-K.; Jung, J.; Cho, J.-J.; Kim, H.-J. Determination of the Oxidation Potentials of Organic Benzene Derivatives: Theory and Experiment. Chem. Phys. Lett. 2003, 368 (5–6), 601-608.

(3) Baik, M.-H.; Friesner, R. A. Computing Redox Potentials in Solution: Density Functional Theory as a Tool for Rational Design of Redox Agents. J. Phys. Chem. A 2003, 106, 7407-7412.

(4) Ong, S. P.; Ceder, G. Investigation of the Effect of Functional Group Substitutions on the Gas-Phase Electron Affinities and Ionization Energies of Room-Temperature Ionic Liquids Ions Using Density Functional Theory. Electrochim. Acta 2010, 55 (11), 3804-3811.

Thank you Francesca, I have the same problem and your question help me.

Dear Francessca and all question followers,

Thanks for this instructive discussion.

I have a question that may be simple.

what is the origin of using thermodynamic cycles for computation of oxidation and reduction potentials in solvents, and if it is problematic to use just G0(solvent) and G+(solvent) after relaxation of molecule in solvent (both in neutral and charged form) to calculate oxidation potential?

Recall that gas-phase partition functions are derived for an ideal gas under the harmonic oscilator rigid rotor approximation and are not necessarily valid in solution.

Have a look at [1] and references within for a discussion on validity of gas-phase partition functions applyed to the frequencies calculated in a dieletric continuum.

[1].Ho, J., Klamt, A. & Coote, M. L. Comment on the Correct Use of Continuum Solvent Models. J. Phys. Chem. A 114, 13442–13444 (2010).

Dear Daniel,

Thanks for your complete answer reference.

Thanks for all your contributions and references.