The correlation between experimental polarized Raman spectra and their density functional theory prediction in the LCAO framework: The R3c LiNbO3 crystal as a test case

Abstract In this study, the polarized Raman spectra of the R 3 c LiNbO 3 crystal are used as a benchmark test for density functional theory (DFT) full periodic boundary conditions linear combination of atomic orbitals (LCAO) calculation of the Raman tensors, according to the implementation in the CRYSTAL software. The theoretical approach used proved to provide excellent results regarding wavenumbers and relative intensities predictions for the transverse optical modes of both A 1 and E symmetry, considerably improving over previously reported data based on the plane waves approach. Overall, the present investigation demonstrates that the LCAO approach, as implemented in the CRYSTAL software, gives excellent results regarding the calculation of Raman tensors and polarized Raman spectra. The possibility to put in correspondence the individual Raman tensors components and bands intensities in the different back‐scattering experimental configurations revealed that the computed Raman tensors are very accurate, not only considering their average values (tensors invariant in the combination suitable for the description of Raman scattering of isotropic materials) but also when the tensors individual components are considered. Based on the present results, a reassignment of the E (TO) modes of the R 3 c LiNbO 3 crystal is proposed, in particular for the 2 E and 9 E modes, which have been a matter of discussion in the recent years.