Water clusters on graphite: Methodology for quantum chemical A priori prediction of reaction rate constants

The properties, interactions, and reactions of cyclic water clusters (H ₂O) _n=1-5 on model systems for a graphite surface have been studied using pure B3LYP, dispersion-augmented density functional tight binding (DFTBD), and integrated ONIOM(B3LYP:DFTB-D) methods. Coronene C ₂₄H ₁₂ as well as polycircumcoronenes C ₉₆H ₂₄ and C ₂₁₆H ₃₆ in monolayer, bilayer, and trilayer arrangements were used as model systems to simulate ABA bulk graphite. Structures, binding energies, and vibrational frequencies of water clusters on mono- and bilayer graphite models have been calculated, and structural changes and frequency shifts due to the water cluster-graphite interactions are discussed. ONIOM(B3LYP:DFTB-D) with coronene and water in the high level and C ₉₀H ₂₄ in the low level mimics the effect of extended graphite π-conjugation on the water-graphite interaction very reasonably and suggests that water clusters only weakly interact with graphite surfaces, as suggested by the fact that water is an excellent graphite lubricant. We use the ONIOM(B3LYP:DFTB-D) method to predict rate constants for model pathways of water dissociative adsorption on graphite. Quantum chemical molecular dynamics (QM/MD) simulations of water clusters and water addition products on the C ₉₆H ₂₄ graphite model are presented using the DFTB-D method. A three-stage strategy is devised for a priori investigations of high temperature corrosion processes of graphite surfaces due to interaction with water molecules and fragments.