Computational electrochemistry: aqueous one-electron oxidation potentials for substituted anilines

Literature Information

Publication Date 2000-03-02
DOI 10.1039/A909076B
Impact Factor 3.676
Authors

Paul Winget, Eric J. Weber, Christopher J. Cramer, Donald G. Truhlar


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Abstract

Semiempirical molecular orbital theory and density functional theory are used to compute one-electron oxidation potentials for aniline and a set of 21 mono- and di-substituted anilines in aqueous solution. Linear relationships between theoretical predictions and experiment are constructed and provide mean unsigned errors as low as 0.02 V over a training set of 13 anilines; the error rises to 0.09 V over a test set of eight additional anilines. A good correlation is also found between oxidation potential and a simple computed property, namely the energy of the highest occupied molecular orbital for neutral anilines in aqueous solution. For the particular case of the substituted anilines, a strong correlation between oxidation potential and pKa is found, and a still stronger correlation between oxidation potential and physical organic descriptors for aromatic substituents is also found, albeit over a reduced data set.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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