Electronic structure, dielectric properties and infrared vibrational spectrum of fayalite: An ab initio simulation with an all-electron Gaussian basis set and the B3LYP functional

Abstract

The electronic structure, the static and high frequency dielectric tensors, and the infrared (IR) spectrum of fayalite Fe2SiO4, the Fe-rich end-member of olivine solid solutions, are explored at an ab initio quantum mechanical level, by using an all-electron Gaussian type basis set, the B3LYP hybrid DFT functional, and the CRYSTAL09 code. Mulliken population analysis and spin density maps illustrate the electronic structure, characterized by a nearly pure d6, high-spin configuration of the transition metal atom. The full set of IR wavenumbers and intensities is computed. The availability of highly accurate synchrotron radiation data (Suto et al., Astron Astrophys 2002, 389, 568) permits a very accurate comparison between simulated and measured quantities, in primis wavenumbers (ν) and oscillator strengths (f). The mean absolute difference ∆v is as small as 4 cm−1, and the maximum absolute difference |Δνmax| never exceeds 12 cm−1, whereas the summed absolute difference ΔF between fexp and fcalc is around 10%. Modes not detected in the experiment turn out to be (i) characterized by low computed intensity, or (ii) very close to a large intense peak. Computed and experimental IR reflectance curves are in striking agreement also. The nature of the vibrational modes is investigated by means of isotopic substitutions, which clarify the participation of the various atomic species to each mode.