Understanding the fundamental chemistry and physics at the interface between carbonate minerals and water is of high interest due to its direct involvement in several broad interdisciplinary topics, including biomineralization, evolution of life and climate, sequestration of contaminants, and CO2 sequestration. Here, the {10-14} facet of calcite is the most extensively studied due to its high stability and frequent natural occurrence. While its atomic structure is widely accepted and involves little if any reconstruction claims[1-4] of reconstruction have emerged over the past three decades, based on experimental and theoretical studies.
Using Density Functional Theory (DFT) we identified the conditions that enable such reconstruction, explained why it arises in specific cases and not in others, and described its underlying mechanism in vacuum and in contact with water.[5] This study has been extended to include the most relevant carbonate phases within the calcite group.
[1] S. Stipp et al. Geochim. Cosmochim. Acta 1991, 55, 1723; 1994, 58, 3023.
[2] A. Rohl et al. Am. Mineral. 2003, 88, 921.
[3] A. Kühnle et al. Langmuir 2010, 26, 8295; J. Phys. Chem. Lett. 2021, 12, 7605; Surf. Sci. 2025, 751, 122598.
[4] J. Heggemann et al. J. Phys. Chem. Lett. 2023, 14, 1983; Phys. Chem. Chem. Phys. 2024, 26, 21365.
[5] R. Demichelis et al., J. Phys. Chem. C, 2025.