Dehydrogenation Free Energy of Co²⁺(aq) from Density Functional Theory-Based Molecular Dynamics

Electron and proton transfers are important steps occurring in chemical reactions. The often used approach of calculating the energy differences of those steps using methods based on geometry optimizations neglects the influence of dynamic effects. To further investigate this issue and inspired by research in water oxidation, we calculate in the present study the dehydrogenation free energy of aqueous Co²⁺, which is the free energy change associated with the first step of the water oxidation reaction mechanism of recently investigated model Co(II)-aqua catalysts. We employ a method based on a thermodynamic integration scheme with strong ties to Marcus theory to obtain free energy differences, solvent reorganization free energies, and dynamic structural information on the systems from density functional theory-based molecular dynamics. While this method is computationally orders of magnitude more expensive than a static approach, it potentially allows for predicting the validity of the approximation of neglecting dynamic effects.