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Ab initio simulation of the IR spectra of pyrope, grossular, and andradite

Abstract:

IR spectra of pyrope Mg3Al2Si3O 12, grossular Ca3Al2Si3O 12 and andradite Ca3Fe2Si3O 12 garnets were simulated with the periodic ab initio CRYSTAL code by adopting an all-electron Gaussian-type basis set and the B3LYP Hamiltonian. Two sets of 17 F1u Transverse Optical (TO) and Longitudinal Optical (LO) frequencies were generated, together with their intensities. Because the generation of LO modes requires knowledge of the high frequency dielectric constant ε∞ and Born effective charges, they were preliminary evaluated by using a finite field saw-tooth model and well localized Wannier functions, respectively. As a by-product, the static dielectric constant ε0 was also obtained. The agreement of the present calculated wavenumbers (i.e. peak positions) with the available experimental data is excellent, in that the mean absolute difference for the full set of data smaller than 8 cm-1. Missing peaks in experimental spectra were found to correspond to modes with low calculated intensities. Correspondence between TO and LO modes was established on the basis of the overlap between the eigenvectors of the two sets and similarity of isotopic shifts; as result, the so called LO-TO splitting could be determined. Animation of the normal modes was employed to support the proposed pairing. © 2008 Wiley Periodicals, Inc.