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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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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author Fileto Rodríguez
Robin Francotte
Beata Taudul
Jianing Wang
Ionut Tranca
Diane Sorgeloos
Enrique Lozano Diz
Monica Calatayud
Frederik Tielens
author_facet Fileto Rodríguez
Robin Francotte
Beata Taudul
Jianing Wang
Ionut Tranca
Diane Sorgeloos
Enrique Lozano Diz
Monica Calatayud
Frederik Tielens
author_sort Fileto Rodríguez
collection DOAJ
description 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.
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issn 0264-1275
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publisher Elsevier
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series Materials & Design
spelling doaj-art-6936b469f63f4ce88d5e4ddbcf33f3812025-08-20T03:22:04ZengElsevierMaterials & Design0264-12752025-08-0125611416510.1016/j.matdes.2025.114165Advanced spectroscopic characterization of calcium carbonate polymorphs: Ab initio dynamic approaches and experimental RamanFileto Rodríguez0Robin Francotte1Beata Taudul2Jianing Wang3Ionut Tranca4Diane Sorgeloos5Enrique Lozano Diz6Monica Calatayud7Frederik Tielens8General Chemistry ALGC – Materials Modelling Group, Vrije Universiteit Brussel, Pleinlaan 2 Brussel, BelgiumGeneral Chemistry ALGC – Materials Modelling Group, Vrije Universiteit Brussel, Pleinlaan 2 Brussel, BelgiumSorbonne Université, MONARIS, CNRS-UMR 8233, 4 Place Jussieu, F-75005 Paris, FranceGeneral Chemistry ALGC – Materials Modelling Group, Vrije Universiteit Brussel, Pleinlaan 2 Brussel, BelgiumGeneral Chemistry ALGC – Materials Modelling Group, Vrije Universiteit Brussel, Pleinlaan 2 Brussel, BelgiumGeneral Chemistry ALGC – Materials Modelling Group, Vrije Universiteit Brussel, Pleinlaan 2 Brussel, BelgiumELODIZ Ltd. High Wycombe, UKSorbonne Université, MONARIS, CNRS-UMR 8233, 4 Place Jussieu, F-75005 Paris, France; Corresponding authors.General Chemistry ALGC – Materials Modelling Group, Vrije Universiteit Brussel, Pleinlaan 2 Brussel, Belgium; Corresponding authors.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.http://www.sciencedirect.com/science/article/pii/S0264127525005854IRRamanAIMDCaCO3PolymorphismDFT
spellingShingle Fileto Rodríguez
Robin Francotte
Beata Taudul
Jianing Wang
Ionut Tranca
Diane Sorgeloos
Enrique Lozano Diz
Monica Calatayud
Frederik Tielens
Advanced spectroscopic characterization of calcium carbonate polymorphs: Ab initio dynamic approaches and experimental Raman
Materials & Design
IR
Raman
AIMD
CaCO3
Polymorphism
DFT
title Advanced spectroscopic characterization of calcium carbonate polymorphs: Ab initio dynamic approaches and experimental Raman
title_full Advanced spectroscopic characterization of calcium carbonate polymorphs: Ab initio dynamic approaches and experimental Raman
title_fullStr Advanced spectroscopic characterization of calcium carbonate polymorphs: Ab initio dynamic approaches and experimental Raman
title_full_unstemmed Advanced spectroscopic characterization of calcium carbonate polymorphs: Ab initio dynamic approaches and experimental Raman
title_short Advanced spectroscopic characterization of calcium carbonate polymorphs: Ab initio dynamic approaches and experimental Raman
title_sort advanced spectroscopic characterization of calcium carbonate polymorphs ab initio dynamic approaches and experimental raman
topic IR
Raman
AIMD
CaCO3
Polymorphism
DFT
url http://www.sciencedirect.com/science/article/pii/S0264127525005854
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