Local Environment and Dynamic Behavior of Fluoride Anions in Silicogermanate Zeolites: A Computational Study of the AST Framework

In silicogermanate zeolites containing double four-ring (d4r) building units, the germanium atoms preferentially occupy the corners of these cube-like units. While this general behaviour is well known, the absence of long-range order precludes a determination of the preferred arrangements of Si and Ge atoms at the corners of d4r cages by means of crystallographic methods. If fluoride anions are present during the synthesis, these are incorporated into the d4r cages. Due to the sensitivity of the ¹⁹F chemical shift to the local environment, NMR experiments can provide indirect insights into the predominant (Si,Ge) arrangements. However, conflicting interpretations have been reported, both with regard to the preference for, or avoidance of, Ge-O-Ge linkages, and concerning the equilibrium position of fluorine inside the cage, where fluorine might either occupy the cage centre or participate in a partly covalent Ge-F bond. In order to shed light on the energetically preferred local arrangements, periodic electronic structure calculations in the framework of dispersion-corrected density functional theory (DFT) were performed. The AST framework was used as a suitable model system, as this zeolite is synthetically accessible across the range of (Si_1-n,Ge_n)O₂ compositions (0 ≤ n ≤ 1). DFT structure optimisations for (Si,Ge)-AST systems containing fluoride anions and organic cations revealed that arrangements of Si and Ge at the cage vertices which maximise the number of Ge-O-Ge linkages are energetically preferred, and that fluorine tends to form relatively short (~2.2 to 2.4 Å) bonds to Ge atoms that are surrounded by Ge-O-Ge linkages. The preference for Ge-O-Ge linkages disappears in the absence of fluorine, pointing to a “templating” effect of the anions. In addition to the prediction of equilibrium structures, DFT-based Molecular Dynamics calculations were performed for selected AST models in order to analyse the dynamics of fluoride anions confined to d4r cages. These calculations showed that the freedom of movement of fluorine varies markedly depending on the local environment, and that it correlates with the average Ge-F distance (short Ge-F bonds = restricted motion). An analysis of the Ge-F radial distribution functions provided no evidence for a coexistence of separate local energy minima at the cage centre and in the proximity of a germanium atom for any of the systems considered. The computational approach pursued in this work provides important new insights into the local structure of silicogermanate zeolites with d4r units, enhancing the atomic-level understanding of these materials. In particular, the findings presented here constitute valuable complementary information that can aid the interpretation of experimental data.