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COMPUTATIONAL ELECTROCHEMISTRY: AQUEOUS ONE-ELECTRON OXIDATION POTENTIALS FOR SUBSTITUTED ANILINES
Winget, P., E J. Weber, C. J. Cramer, AND D. G. Truhlar. COMPUTATIONAL ELECTROCHEMISTRY: AQUEOUS ONE-ELECTRON OXIDATION POTENTIALS FOR SUBSTITUTED ANILINES. PHYSICAL CHEMISTRY CHEMICAL PHYSICS 2(6):1231-1239, (2000).
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 pK(a)
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.
Record Details:Record Type: DOCUMENT (JOURNAL/PEER REVIEWED JOURNAL)
Organization:U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
NATIONAL EXPOSURE RESEARCH LABORATORY
ECOSYSTEMS RESEARCH DIVISION
PROCESSES & MODELING BRANCH