The evaluation of solvation energies is a great challenge. We focus here on an organic molecule chemisorbed at a metal-liquid interface, as a prototypical system, essential in tribology, electrochemistry and heterogeneous catalysis. We compare an established implicit solvation scheme with a strategy based on molecular mechanics (MM) free energy perturbation (FEP) seeded by QM computations. First, we benchmark the approaches against experimental hydration energies of standard (organic) molecules and find acceptable errors in the order of 0.06 eV (1.3 kcal mol^-1). Then, the impact of various parameters on the solvation energy of an adsorbate have been assessed on a typical system of interest, levulinic acid adsorbed at a Ru(0001)/water interface. We identify the need for dipole corrections or symmetric slabs when including solvation effects on metallic surfaces. The MM-FEP scheme is revealed to be as reliable as the implicit solvent for water. In the case of levulinic acid, both PCM and MM-FEP agree that the bulk solvation effect is not sufficient to change the adsorption mode from bidentate to mono-dentate, despite the fact that the COOH group is desolvated in the bidentate case. MM-FEP has the great advantage of being more easily generalized to other solvents and to be further improved which will be particularly useful to study solvent and (counter-)ion effects on interfacial reactions.

Alcohol oxidation by O2 to carboxylic acid can be operated in water using noble-metal catalysts, but relies on the undesirable addition of a base such as sodium hydroxide. Using periodic density functional theory (DFT), we built a model including the chemisorption of hydroxide anion at the metal/water interface to rationalize the pivotal role of the added base on the catalytic activity. We demonstrate that the role of the base is to polarize the surface and that a similar promotion could be obtained by tuning the electronic properties of additives, alloy, and support.

Zeolites are essential materials to industry due to their adsorption and catalytic properties. The best current approach to prepare a targeted zeolite still relies on trial and error's synthetic procedures since a rational understanding of the impact of synthesis variables on the final structures is still missing. To discern the role of a variety of organic templates, we perform simulations of the early stages of condensation of silica oligomers by combining DFT, Brønsted-Evans-Polanyi relationships and kinetic Monte Carlo simulations. We investigate an extended reaction path mechanism including 258 equilibrium reactions and 242 chemical species up to silica octamers, comparing the computed concentrations of Si oligomers with ²⁹ SI NMR experimental data. The effect of the templating agent is linked to the modification of the intramolecular H-bond network in the growing oligomer, which produces higher concentration of 4-membered ring intermediates, precursors of the key double-four ring building blocks present on more than 39 known zeolite topologies.