High-temperature Raman spectroscopy and quasi-harmonic lattice dynamic simulation of diopside

Abstract

We investigated the lattice vibrational properties and lattice dynamical behaviour of diopside by combining laser micro-Raman spectroscopic measurements with quasi-harmonic lattice dynamic simulation using a transferable interatomic potential. We obtained polarized Raman spectra from a Fe-poor natural diopside and the temperature dependencies of the Raman modes to 1125 K from high-temperature Raman spectra of a Fe-poor and a Fe-rich natural diopside. The various modes display different temperature dependencies: from −0.021 cm−1/K to −0.004 cm−1/K. The temperature shift of low frequency modes is generally higher. A comparison of experimentally determined frequencies and symmetries of vibrational modes of the optical type (Raman and infrared) obtained in this and earlier studies with those calculated by us suggests that a consistent characterization of the vibrational properties was achieved. The good agreement between the experimental and simulated data on the temperature-dpendencies of the Raman modes (within 5%), crystal structure (2%), bulk modulus (5%), volume thermal expansivity (6%), and constant volume heat capacity (0.2%) testifies to the applicability of the transferable interatomic potential and the lattice dynamic model to predicting the vibrational, physical, and thermodynamic properties. The simulated properties from the lattice dynamic calculations are very similar to those obtained by molecular dynamic calculations with the same potential model.