Nonperturbative Simulation of Anharmonic Rattler Dynamics in Type-I Clathrates with Vibrational Dynamical Mean-Field Theory

We use vibrational dynamical mean-field theory (VDMFT) to study the vibrational structure of type-I clathrate solids, specifically X₈Ga₁₆Ge₃₀, where X=Ba,Sr. These materials are cage-like chemical structures hosting loosely bound guest atoms, resulting in strong anharmonicity, short phonon lifetimes, and ultra-low thermal conductivities. Presenting the methodological developments necessary for this first application to three-dimensional, atomistic materials, we validate our approach through comparison to molecular dynamics simulations and show that VDMFT is extremely accurate at a fraction of the cost. We find that anharmonicity causes rattler modes to shift up in frequency by 50% (10 cm⁻¹) and to have lifetimes of less than 1 ps. Furthermore, we analyze the phonon self-energy and find that anharmonicity mixes guest rattling modes and cage acoustic modes, significantly changing the character of the harmonic phonons.