Atomistic Insights into Silicate Dissolution of Metakaolinite under Alkaline Conditions: <i>Ab Initio</i> Quantum Mechanical Investigation

This study employs computational chemistry to investigate the detailed mechanisms behind the dissolution of thermally activated clays, which are emerging as promising supplementary cementitious materials (SCM) for enhancing concrete properties and reducing carbon footprint. Specifically, the study employs a first-principles methodology for obtaining activation energies (Δ<i>E</i>_a) involved in the dissolution of metakaolinite (MK) silicate units using NaOH and KOH activators. The investigation includes considerations of hydrolyzing oxo-bridging covalent bonds, van der Waals (vdW) interactions, and the influence of water molecules surrounding alkali cations. The study employs the enhanced dimer method within density functional theory (DFT) to propose four models for determining the activation energies required to break oxo-bridging bonds. The results demonstrate that KOH generally requires lower activation energies than NaOH, particularly when considering vdW interactions. They also highlight the lower activation energy required for commencing the dissolution of silicate units and emphasize the significance of the hydration shell around cations. The proposed methodology contributes to establishing a systematic database of atomistic activation energies, essential for atomistic kinetic Monte Carlo upscaling and mesoscopic forward dissolution rate calculations in clays. This holds relevance in understanding their reactivity within cementitious materials.