Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
1250607 | Vibrational Spectroscopy | 2011 | 8 Pages |
Very accurate vibrational spectra of silicates are obtained from DFT calculations if the appropriate Hamiltonian is used. Theoretical considerations suggest that the Hartree–Fock component of ACM1 hybrid functionals should be 1/6 instead of 1/4 for this class of compounds. When applied to the PBE functional this removes the scaling error of the calculated vibrational frequencies. Calculations using this PBE(n = 6) functional in combination with optimized Gaussian basis sets result in very small remaining deviations between observed and calculated Raman shifts, with standard uncertainties of ≈3.5 cm−1, maximum deviations of ≈10 cm−1, and no significant systematic trends. This has been confirmed for a wide range of silicate structures, for which high-quality Raman spectra have been published: forsterite α-Mg2SiO4 (nesosilicate), γ-Y2Si2O7 (sorosilicate), K2Ca3Si3O10 (oligosilicate), K2Ca4Si8O21 (phyllosilicate), and α-quartz SiO2 (tectosilictae).