Density functional modelling of silicate and aluminosilicate dimerisation solution chemistry

Common throughout sol-gel chemistry, including zeolite synthesis, aluminosilicate glass formation and geopolymerisation, is the process of inorganic oxide polymerisation and deprotonation. In this investigation, some of the fundamental reactions occurring during zeolite synthesis and geopolymerisation at high pH are investigated using density functional theory (DFT), and are compared with: (i) existing values reported in the literature, and (ii) new and previously published DFT-derived data for similar silicate reactions at near-neutral pH. From the results it is seen that the energetics of deprotonation and dimerisation reactions depend greatly on the pH value, and these results correlate well with existing experimental values and trends. Hence, this investigation exemplifies that an accurate replication of the solution environment is crucial for obtaining useful theoretical results for species dissolved in non-ideal environments.