A method to calculate the one-electron reduction potentials for nitroaromatic compounds based on gas-phase quantum mechanics
✍ Scribed by Kathy L. Phillips; Stanley I. Sandler; Pei C. Chiu
- Publisher
- John Wiley and Sons
- Year
- 2010
- Tongue
- English
- Weight
- 202 KB
- Volume
- 32
- Category
- Article
- ISSN
- 0192-8651
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✦ Synopsis
Abstract
Nitroaromatic compounds (NACs) are widespread environmental contaminants, and the one‐electron reduction potential (E) is an important parameter used in modeling their environmental fate. We have identified a method that is both accurate and efficient to predict E values for NACs, using gas‐phase quantum mechanics (QM) calculations combined with empirical correlations. First, the adiabatic electron affinity (EA) at 0 K is calculated using the B98/MG3S method, and the predictions are scaled by a factor of 0.802 to account for systematic errors in the density functional calculations. Second, the E values are predicted from a linear correlation between E and EA. Using this method, E values were predicted with a mean absolute deviation from measured values of 0.021 V for the 14 NACs used to obtain the correlation and 0.029 V for six additional NACs. This represents a substantial improvement in accuracy over predictions by other QM methods, which are affected by large errors in solvation or aqueous‐phase calculations for some compounds. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010.