One-electron reduction potentials from chemical structure theory calculations

Eric J. Bylaska, Alexandra J. Salter-Blanc, Paul G. Tratnyek

Research output: Chapter in Book/Report/Conference proceedingConference contribution

12 Scopus citations

Abstract

Many redox reactions of importance in aquatic chemistry involve elementary steps that occur by single-electron transfer (SET). This step is often the first and rate limiting step in redox reactions of environmental contaminants, so there has been a great deal of interest in the corresponding one-electron reduction potentials (E1). Although E1 can be obtained by experimental methods, calculation from first-principles chemical structure theory is becoming an increasingly attractive alternative. Sufficient data are now available to perform a critical assessment of these methods-and their results-for two types of contaminant degradation reactions: dehalogenation of chlorinated aliphatic compounds (CACs) and reduction of nitro aromatic compounds (NACs). Early datasets containing E1's for dehalogenation of CACs by dissociative SET contained a variety of errors and inconsistencies, but the preferred datasets show good agreement between values calculated from thermodynamic data and quantum mechanical models. All of the datasets with E1's for reduction of NACs by SET are relatively new, were calculated with similar methods, and yet yield a variety of systematic differences. Further analysis of these differences is likely to yield computational methods for E1's of NAC nitro reduction that are similar in reliability to those for CAC dechlorination. However, comparison of the E1 data compiled here with those calculated with a more universal predictive model (like SPARC) highlight a number of challenges with implementation of models for predicting properties over a wide range of chemical structures.

Original languageEnglish (US)
Title of host publicationAquatic Redox Chemistry
PublisherAmerican Chemical Society
Pages37-64
Number of pages28
ISBN (Print)9780841226524
DOIs
StatePublished - Jan 1 2011

Publication series

NameACS Symposium Series
Volume1071
ISSN (Print)0097-6156
ISSN (Electronic)1947-5918

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

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    Bylaska, E. J., Salter-Blanc, A. J., & Tratnyek, P. G. (2011). One-electron reduction potentials from chemical structure theory calculations. In Aquatic Redox Chemistry (pp. 37-64). (ACS Symposium Series; Vol. 1071). American Chemical Society. https://doi.org/10.1021/bk-2011-1071.ch003