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Cited by 311

The DOI matches its Crossref record; 34 of the 34 references it cites were found in a registry or an index.

Calculation of One-Electron Redox Potentials Revisited. Is It Possible to Calculate Accurate Potentials with Density Functional Methods?

Roy, Lindsay E., Jakubikova, Elena, Guthrie, M. Graham, Batista, Enrique R.·2009·The Journal of Physical Chemistry A
DOI 10.1021/jp811388w
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Abstract

Density Functional calculations have been performed to calculate the one-electron oxidation potential for ferrocene and the redox couples for a series of small transition metal compounds of the first-, second-, and third-row elements. The solvation effects are incorporated via a self-consistent reaction field (SCRF), using the polarized continuum model (PCM). From our study of seven different density functionals combined with three different basis sets for ferrocene, we find that no density functional method can reproduce the redox trends from experiment when referencing our results to the experimental absolute standard hydrogen electrode (SHE) potential. In addition, including additional necessary assumptions such as solvation effects does not lead to any conclusion regarding the appropriate functional. However, we propose that if one references their transition metal compounds results to the calculated absolute half-cell potential of ferrocene, they can circumvent the additional assumptions necessary to predict a redox couple. Upon employing this method on several organometallic and inorganic complexes, we obtained very good correlation between calculated and experimental values (R(2) = 0.97), making it possible to predict trends with a high level of confidence. The hybrid functional B3LYP systematically underestimates the redox potential; however, the linear correlation between DFT and experiment is good (R(2) = 0.96) when including a baseline shift. This protocol is a powerful tool that allows theoretical chemists to predict the redox potential in solution of several transition metal complexes a priori and aids in the rational design of redox-active catalysts.

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Metadata

Authors
Roy, L. E., Jakubikova, E., Guthrie, M. G., & Batista, E. R.
Venue
The Journal of Physical Chemistry A
Publisher
American Chemical Society (ACS)
Published
2009-05-21
Volume
113
Issue
24
Pages
6745-6750
ISSN
  • 1089-5639 (ISSN-L)
  • 1520-5215
DOI
10.1021/jp811388w
OpenAlex
W1997060636
Cited by
311
References
34
FWCI
9.85
Type
journal article
Language
en
Open access
closed

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