Science Inventory

COMPUTATIONAL ELECTROCHEMISTRY: AQUEOUS ONE-ELECTRON OXIDATION POTENTIALS FOR SUBSTITUTED ANILINES

Citation:

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).

Description:

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)
Product Published Date: 03/01/2000
Record Last Revised: 12/22/2005
Record ID: 64934

Organization:

U.S. ENVIRONMENTAL PROTECTION AGENCY

OFFICE OF RESEARCH AND DEVELOPMENT

NATIONAL EXPOSURE RESEARCH LABORATORY

ECOSYSTEMS RESEARCH DIVISION

PROCESSES & MODELING BRANCH