Resolving Point Defects in the Hydration Structure of Calcite (10.4) with Three-Dimensional Atomic Force Microscopy

2018

It seems natural to assume that defects at mineral surfaces critically influence interfacial processes such as the dissolution and growth of minerals in water. The experimental verification of this claim, however, is challenging and requires real-space methods with utmost spatial resolution, such as atomic force microscopy (AFM). While defects at mineral-water interfaces have been resolved in 2D AFM images before, the perturbation of the surrounding hydration structure has not yet been analyzed experimentally. In this Letter, we demonstrate that point defects on the most stable and naturally abundant calcite (10.4) surface can be resolved using high-resolution 3D AFM-even within the fifth h…

Does the Structural Water within Gypsum Remain Crystalline at the Aqueous Interface?

2021

Probing the Multiple Structures of Vaterite through Combined Computational and Experimental Raman Spectroscopy.

2014

First-principles Raman spectra have been computed for several new vaterite structural models that have been recently proposed, and compared with spectra recorded on a set of biogenic, geological and synthetic samples. This set includes new measurements collected on Herdamania momus spicules (Great Barrier Reef, Queensland, Australia), which are known to have purity and crystallinity that are higher than for other biogenic samples. Overall, due to the close structural connection between the various models, the computed Raman spectra are found to be broadly similar. However, the spectra obtained for the two most stable models (monoclinic C2 and trigonal P3221, corresponding to two different p…

Where Is the Most Hydrophobic Region? Benzopurpurine Self-Assembly at the Calcite–Water Interface

2017

Control of molecular self-assembly at solid–liquid interfaces is challenging due to the complex interplay between molecule–molecule, molecule–surface, molecule–solvent, surface–solvent, and solvent–solvent interactions. Here, we use in-situ dynamic atomic force microscopy to study the self-assembly of Benzopurpurine 4B into oblong islands with a highly ordered inner structure yet incommensurate with the underlying calcite (10.4) surface. Molecular dynamics and free energy calculations provide insights by showing that Benzopurpurine 4B molecules do not anchor to the surface directly but instead assemble on top of the second hydration layer. This seemingly peculiar behavior was then rationali…