Soft phonon modes in rutile TiO${}_2$

Abstract

The lattice dynamics of TiO${}_2$ in the rutile crystal structure was studied by a combination of thermal diffuse scattering, inelastic x-ray scattering and density functional perturbation theory. We experimentally confirm the existence of an anomalous soft transverse acoustic mode with energy minimum at q = (1/2 1/2 1/4). The phonon energy landscape of this particular branch is reported and compared to the calculation. The harmonic calculation underestimates the phonon energies but despite this the shape of both the energy landscape and the scattering intensities are well reproduced. We find a significant temperature dependence in energy of this transverse acoustic mode over an extended region in reciprocal space which is in line with a substantially anharmonic mode potential-energy surface. The reported low energy branch is quite different from the ferroelectric mode that softens at the Brillouin zone center and may help explain anomalous convergence behavior in calculating TiO${}_2$ surface properties.

References in corpus (2)

• Entropy driven stabilization of energetically unstable crystal structures explained from first principles theory
• Phonon quarticity induced by changes in phonon-tracked hybridization during lattice expansion and its stabilization of rutile TiO${}_2$

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• Introduction to High-Resolution Inelastic X-Ray Scattering
• Ab initio based description of the unusual temperature increase of the electric field gradient at Ti sites in rutile TiO2
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• Strain-induced structural change and nearly-commensurate diffuse scattering in the model high-temperature superconductor HgBa${}_2$CuO${}_{4+\delta }$