Computational investigations of structural and energetic changes in chemical reactions at metal/water interfaces pose a unique challenge because of great computational costs associated with quantum chemical calculations and adequate phase-space sampling. A practical solution to this challenge is a hybrid QM/MM approach that can provide a reasonably accurate energetic description of the complex metal/water system while offering a computational speedup of multiple orders of magnitude. In this talk, we present a strategy that combines planewave density functional theory (DFT), periodic electrostatic embedded cluster method (PEECM) and classical molecular dynamics calculations with the QM/MM free-energy perturbation (FEP) methodology to enable an accurate determination of free-energies of reaction and activation free-energy barriers at periodic metal/water interfaces. Application to C-C cleavage in double-dehydrogenated ethylene glycol on Pt (111) surface will also be discussed.

Computational investigation of reactions at metal/water interfaces

245th National Meeting (2013)

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