Density functional modeling of the binding energies between aluminosilicate oligomers and different metal cations

TL;DR

This study uses density functional theory to calculate and analyze the binding energies between aluminosilicate oligomers and various metal cations, revealing correlations with ionic properties and aiding material design.

Contribution

It introduces a computational approach to predict cation-aluminosilicate interactions, enabling rapid estimation of binding energies based on ionic potential and field strength.

Findings

Binding energies vary with cation type and aluminosilicate species.

Strong correlation between binding energies and ionic potential/field strength.

Polynomial models accurately predict binding energies (R2 > 0.99).

Abstract

Interactions between negatively charged aluminosilicate species and positively charged metal cations are critical to many important engineering processes and applications, including sustainable cements and aluminosilicate glasses. In an effort to probe these interactions, here we have calculated the pair-wise interaction energies (i.e., binding energies) between aluminosilicate dimer/trimer and 17 different metal cations using a density functional theory (DFT) approach. Analysis of the DFT-optimized structural representations for the clusters (dimer/trimer + cation) shows that their structural attributes (e.g., interatomic distances) are generally consistent with literature observations on aluminosilicate glasses. The DFT-derived binding energies are seen to vary considerably depending on the type of cations (i.e., charge and ionic radii) and aluminosilicate species (i.e., dimer or trimer). A survey of the literature reveals that the difference in the calculated binding energies between different cations can be used to explain many literature observations on the impact of cations on materials properties (e.g., glass corrosion, mineral dissolution, and ionic transport). Analysis of all the DFT-derived binding energies reveals that the correlation between these energy values and the ionic potential and field strength of the cations are well captured by 2nd order polynomial functions (R2 values of 0.99-1.00 are achieved for regressions). Given that the ionic potential and field strength of a given metal cation can be readily estimated using well-tabulated ionic radii available in the literature, these simple polynomial functions would enable rapid estimation of the binding energies of a much wider range of cations with the aluminosilicate dimer/trimer, providing guidance on the design and optimization of sustainable cements and aluminosilicate glasses and their associated applications.