Work

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

Year: 2025

Type: article

Abstract: This work introduces an innovative approach to the computational characterization of calcium carbonate polymorphs, critical materials in both natural and technological contexts. By leveraging cutting-edge quantum chemical calculations and the autocorrelation function (ACF) formalism, this study provides unprecedentedly accurate Raman spectra for calcite, aragonite, and vaterite, enhancing our ability to link structural and spectroscopic properties. For the first time, Voronoi radical tessellation is applied to ionic systems, yielding high-quality electromagnetic properties. This advanced protocol surpasses traditional static harmonic methods, particularly in reproducing relative intensity spectra—a known challenge in vibrational analysis. Our findings reveal that optimizing atomic radii in the ACF scheme significantly improves intensity prediction. Alongside Raman spectra, we present computed infrared spectra and X-ray diffractograms for each structure, offering clarity on debated peak assignments in vaterite. This work represents a transformative step forward in accurately modeling and interpreting the spectroscopic behavior of calcium carbonates, pushing the boundaries of computational materials science.

Source: Materials & Design

DOI: 10.1016/j.matdes.2025.114165