Advanced spectroscopic characterization of calcium carbonate polymorphs: Ab initio dynamic approaches and experimental Raman

The vibrational spectroscopic properties of crystalline anhydrous calcium carbonate polymorphs, i.e. calcite, aragonite and vaterite, are computed with state-of-the-art computational techniques. We present a refined protocol that significantly enhances the quality of spectra obtained via the autocor...

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Bibliographic Details
Main Authors: Fileto Rodríguez, Robin Francotte, Beata Taudul, Jianing Wang, Ionut Tranca, Diane Sorgeloos, Enrique Lozano Diz, Monica Calatayud, Frederik Tielens
Format: Article
Language:English
Published: Elsevier 2025-08-01
Series:Materials & Design
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Online Access:http://www.sciencedirect.com/science/article/pii/S0264127525005854
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Summary:The vibrational spectroscopic properties of crystalline anhydrous calcium carbonate polymorphs, i.e. calcite, aragonite and vaterite, are computed with state-of-the-art computational techniques. We present a refined protocol that significantly enhances the quality of spectra obtained via the autocorrelation function formalism, particularly for ionic materials. For the first time, Voronoi Radical Tessellation (VRT) is applied for the computation of electromagnetic properties of ionic systems in combination with Bader’s Quantum Theory of Atoms In Molecules (QTAIM). The use of the later allows for the determination of accurate Voronoi radii, making VRT completely ab initio. Our findings lead the way for the accurate computation of vibrational spectra in materials where anharmonicity, temperature or conformational variety have a considerable impact in the resulting spectrum. This work represents a step forward in accurately modeling and interpreting the spectroscopic behavior of ionic materials, pushing the boundaries of computational materials science.
ISSN:0264-1275