A method to calculate the one-electron reduction potentials for nitroaromatic compounds based on gas-phase quantum mechanics
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Updated: Jun 10, 2026

Using Cyclic Voltammetry, UV-Vis-NIR, and EPR Spectroelectrochemistry to Analyze Organic Compounds
Published on: October 18, 2018
Kathy L Phillips1, Stanley I Sandler, Pei C Chiu
1Department of Chemical Engineering, Center for Molecular and Engineering Thermodynamics, University of Delaware, 150 Academy Street, Newark, Delaware 19716, USA.
Abstract:
Nitroaromatic compounds (NACs) are widespread environmental contaminants, and the one-electron reduction potential (E oH) is an important parameter used in modeling their environmental fate. We have identified a method that is both accurate and efficient to predict E oH 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 oH values are predicted from a linear correlation between E oH and EA. Using this method, E oH 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.
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