Aqueous one-electron oxidation processes are widely important in the aquatic, marine, aerosol, and biological sciences.  However for many organic substances that are susceptible to oxidation, thermodynamic information about redox-mediated transformations are lacking. We aim to develop a priori methods to calculate oxidation potentials and related thermodynamic properties of organic compounds. For a small test set of diverse structures, we estimated one-electron oxidation potentials and reorganization energies using explicitly solvated QM/MM molecular dynamics trajectories. This was combined with classically generated corrections to the linear response approximation and benchmark level corrections to the gas phase ionization potential. Without parameterization to any experimental data, resulting predictions of oxidation potentials and radical cation solvation energies were significantly more accurate than those given by implicit solvation models. Properly developed modeling methods can advance the fundamental understanding of oxidation processes involving organic contaminants, natural organic matter, and biological molecules in natural and engineered aqueous systems.

Quantum chemical estimation of oxidation potentials of environmental organic contaminants in aqueous systems

248th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.