The computational estimation of redox potentials is important for the design of new materials for energy technologies. Several methods are commonly used to estimate redox potentials, including the Born-Haber Cycle, S<sub>0</sub>–D<sub>0</sub> energy difference approximation (EDA) and the molecular orbital energy approximation (MOEA). One problem that often come across when employing these methods is how to account for the solute-solvent interactions. In the present study, we use the EDA and MOEA to calculate the redox potentials of a series of small organic molecules in aqueous solutions. To account for solute-solvent interactions we explore if incorporating explicit solvent molecules can yield more accurate redox potentials. Calculations were performed using B3LYP/6-31G(d) and the semi-empirical Hamiltonian (PM6). Our results show that adding a few explicit water molecules to the model improves the calculated redox potentials for some systems, but that using a continuum solvent model is enough for most cases.

Incorporation of explicit water molecules to calculate standard redox potentials of organic molecules in aqueous solutions

2019 Spring National Meeting

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