Understanding the mechanism and kinetics of chemical reactions in a complex fluctuating environment is a challenge. We demonstrate how ab initio molecular dynamics simulations of chemical reactions in aqueous and methanol solution provides novel insight into the role of solvent molecules in the mechanism and kinetics of reactions. In our approach we combine a density functional theory (DFT) description of the electronic structure with advanced free-energy and path-sampling molecular dynamics techniques. This provides an accurate and realistic picture of the thermodynamics, mechanism and kinetics of the reaction pathways. For selected proto-type example reactions we show how solvent molecules play an active role in the reaction by participating via hydrogen bonding, donating protons, or mediating proton-transfer processes. This yields a picture of the free-energy profile and reaction mechanism that is fundamentally different from that predicted by gas-phase calculations without explicit solvent.

Modeling chemical reactions in protic solvents

256th National Meeting (2018)

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