Theory of the phonon spectrum in host-guest crystalline solids with avoided crossing

Abstract

We develop an analytical model to describe the phonon dispersion relations of host-guest lattices with heavy guest atoms (rattlers). Crucially, the model also accounts for phonon damping arising from anharmonicity. The spectrum of low energy states contains acoustic-like and (soft) optical-like modes, which display the typical avoided crossing, and which can be derived analytically by considering the dynamical coupling between host lattice and guest rattlers. Inclusion of viscous anharmonic damping in the model allows us, for the first time, to compute the vibrational density of states (VDOS) and the specific heat, unveiling the presence of a boson peak (BP) linked to an anharmonicity-smeared van Hove singularity. Upon increasing the coupling strength between the host and the guest dynamics, and by decreasing the energy of the soft optical modes, the BP anomaly becomes stronger and it moves towards lower frequencies. Moreover, we find a robust linear correlation between the BP frequency and the energy of the soft optical-like modes. This framework provides a useful model for tuning the thermal properties of host-guest lattices by controlling the VDOS, which is crucial for optimizing thermal conductivity and hence the energy conversion efficiency in these materials.