Ab initio modeling of Raman and infrared spectra of calcite

Abstract

Calcite is the most thermodynamically stable polymorphic phase of the CaCO3 crystal. It is widely used in modern optical instruments operating in the infrared and visible wavelengths of electromagnetic radiation. In particular, due to its anisotropic properties, calcite is used in polarization optics devices. Ab initio quantum mechanical modeling of the Raman and infrared spectra of calcite makes it possible to better understand the structure and nature of the chemical bonds of the compound, and find the optimal conditions for the effective use of unique properties of calcite in photonics tools. The calculations are performed within the framework of the density functional theory in the CRYSTAL program, using the “hybrid” B3LYP functional and the all-electronic bases of the STO-6G, PO-TZVP and BSD atomic orbitals of the Gaussian type. The obtained results for the elastic constants, Raman and infrared spectra of calcite agree satisfactorily with the available experimental data for the basic sets of POB-TZVP and BSD.