Local order in natural sanidine disentangled via single crystal diffuse scattering

Abstract

Natural sanidine commonly preserves metastable chemical disorder at ambient conditions, but the local structural correlations associated with this disorder remain poorly understood due to a reliance on average-structure analysis alone. Here, we investigate single-crystal diffuse scattering in a natural sanidine from Drachenfels, Germany, with consistent observations across additional samples from Laacher See, Germany, and Vesuvio, Italy. The diffraction data reveal pronounced anisotropic diffuse features, including characteristic bowtie-like intensity distributions in reciprocal space. To resolve the origin of these features, we combine three-dimensional difference pair distribution function (3D-$Δ$PDF) analysis with force-field calculations and Monte Carlo modelling. The 3D-$Δ$PDF shows correlated deviations from the average structure and indicates a strong coupling between occupational and displacive disorder. Force-field calculations demonstrate that the aluminosilicate framework responds strongly to the local alkali occupancy, with the largest structural variation occurring along the $a$ direction. Guided by these observations, we construct a disorder model in which K/Na occupational short-range order is combined with chemically constrained Al/Si distributions and local framework relaxations. The model reproduces the main experimental diffuse-scattering features and shows that the bowtie-like diffuse scattering arises from correlated framework distortions driven primarily by local K/Na order.