Phonon order and reststrahlen bands of polar vibrations in crystals with monoclinic symmetry

TL;DR

This paper analyzes the order and polarization-dependent structure of polar phonon modes and reststrahlen bands in monoclinic crystals, revealing the pairing of transverse and longitudinal modes and their impact on optical properties.

Contribution

It introduces a new eigendielectric displacement vector approach to determine phonon mode order and reststrahlen band structure in monoclinic materials, supported by experimental and DFT data.

Findings

Phonon modes form pairs of transverse and longitudinal modes.

Outer mode pairs create polarization-dependent reststrahlen bands.

Inner mode pairs lead to polarization-independent bands.

Abstract

We derive from an eigendielectric displacement vector summation approach the frequency order of the polar phonon modes and the polarization-dependent structure of the reststrahlen bands within the monoclinic plane of materials with monoclinic crystal symmetry. We show that phonon modes occur in associated pairs of transverse and longitudinal optical modes, and that pairs either belong to inner or outer phonon modes. Inner mode pairs are nested within outer mode pairs. Outer mode pairs cause polarization-dependent reststrahlen bands. Inner mode pairs cause polarization-independent reststrahlen bands. The directional limiting frequencies within the Born-Huang approach are bound to within outer mode regions not occupied by inner mode pairs. Hence, an unusual phonon mode order can occur where both lower-frequency as well as upper-frequency limits for the directional modes can be both transverse and/or longitudinal modes. We exemplify our findings using experimental data for the recently unraveled case of monoclinic symmetry $\beta$-Ga$_2$O$_3$ [Phys. Rev. B~\textbf{93}, 125209 (2016)] and demonstrate excellent agreement with results from density functional theory calculations.