A Method to Calculate the One-Electron Reduction Potentials for Nitroaromatic Compounds Based on Gas-Phase Quantum Mechanics

作者：Phillips Kathy L; Sandler Stanley I^*; Chiu Pei C

来源：Journal of Computational Chemistry, 2011, 32(2): 226-239.

DOI：10.1002/jcc.21608

• one-electron reduction potential
• nitroaromatic compounds
• electron affinity
• solvation
• quantum mechanics

Nitroaromatic compounds (NACs) are widespread environmental contaminants, and the one-electron reduction potential (E(H)(degrees)) is an important parameter used in modeling their environmental fate. We have identified a method that is both accurate and efficient to predict E(H)(degrees) 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 Eo H values are predicted from a linear correlation between E(H)(degrees) and EA. Using this method, E(H)(degrees) 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.

• 出版日期2011-1-30