First‐principles study of vibrational properties of TiSiO4 clusters

Abstract

AbstractFirst‐principles calculations were performed to investigate the vibrational properties of monomers and dimers of titania, silica, and titania‐silica hybrid clusters. Density functional theory‐based formulism was employed to optimize the geometry at the B3LYP level and calculate the infrared and Raman spectra of the clusters by using the GGA‐PBE exchange‐correlation functional. It was found that the vibrational spectra of Ti2O4, Si2O4, and TiSiO4 hybrid clusters provide fingerprint information about structures and structural transitions during the formation of cluster structures. In the case of Si2O4 the mode at 410 cm−1 exhibited the largest vibration of Si atoms, whereas in the case of Ti2O4 the mode at 442 cm−1 exhibited the largest vibration of Ti atoms. The hybrid cluster TiSiO4 was structured using two different methods to explore the effects of starting geometry on the structures and vibrational modes of the clusters. The structural properties of the clusters remained unchanged but vibrational modes were found to be different. It is found that Si shows notable vibrations, but the metal atom Ti merely shows any vibration in the case of TiSiO4 hybrid clusters. The low and intermediate frequency modes were stiffened, whereas the three highest frequency modes were softened when the starting geometry of the hybrid clusters was changed from Si2O4 to Ti2O4.