Heat Transport Mechanisms in MOF-5

Abstract

We find that MOF-5 supports both long-lived phonons and linker vibrations whose split spectra signal a breakdown of the phonon quasiparticle approximation. Combining mode-projected molecular dynamics spectra with spectral Wigner heat transport, we resolve two contrasting transport channels: low-frequency particle-like phonon propagation decreases strongly from 200 to 500 K, whereas wave-like phonon coherence remains nearly constant and supplies about half the intrinsic conductivity at 500 K. A phenomenological extrinsic scattering model provides a plausible explanation for the discrepancy between calculated and measured conductivities in terms of both its magnitude and temperature dependence. We also identify signatures of phonon quasiparticle breakdown in the linker vibrations of ZIF-8 and HKUST-1, indicating that this feature extends to other metal-organic frameworks.