Soft phonon modes in rutile TiO$_2$

TL;DR

This study combines experimental and theoretical methods to investigate soft phonon modes in rutile TiO$_2$, revealing an anomalous transverse acoustic mode with significant temperature dependence and anharmonicity.

Contribution

It provides the first combined experimental and computational analysis of the soft transverse acoustic phonon mode in rutile TiO$_2$, highlighting its anharmonic behavior and potential impact on surface property calculations.

Findings

Confirmed the existence of a soft transverse acoustic mode at q = (1/2 1/2 1/4).

Observed significant temperature dependence of the phonon energy.

Harmonic calculations underestimate phonon energies but reproduce the energy landscape shape.

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.