Reversible Hydration of α-Dicarbonyl Compounds from Ab Initio Metadynamics Simulations: Comparison between Pyruvic and Glyoxylic Acids in Aqueous Solutions

Glyoxylic and pyruvic oxoacids are widely available in the atmosphere as gas-phase clusters and particles or in wet aerosols. In aqueous conditions, they undergo interconversion between the unhydrated oxo and gem-diol forms, where two hydroxyl groups replace the carbonyl group. We here examine the hydration equilibrium of glyoxylic and pyruvic acids with first-principles simulations in water at ambient conditions using ab initio metadynamics to reconstruct the corresponding free-energy landscapes. The main results are as follows: (i) our simulations reveal the high conformational diversity of these species in aqueous solutions. (ii) We show that gem-diol is strongly favored in water compared to its oxo counterpart by 29 and 16 kJ/mol for glyoxylic and pyruvic acids, respectively. (iii) From our atomic-scale simulations, we present new insights into the reaction mechanisms with a special focus on hydrogen-bond arrangements and the electronic structure of the transition state.