Peishi Cheng1 Austin Minnich2 Nina Shulumba2

1, Materials Science, California Institute of Technology, Pasadena, California, United States
2, California Institute of Technology, Pasadena, California, United States

Thermally conductive molecular crystals are of fundamental and practical interest in part because they are unlike typical complex crystals, which conduct heat poorly owing to their large phonon scattering phase space. While molecular crystals with high thermal conductivity in the range of tens of Wm-1K-1 have been known experimentally for decades, the microscopic origin of this property has remained unclear. Ab-initio methods that have been successfully applied to simple crystals have proved difficult to adapt to molecular crystals due to quantum nuclear motion and their complex primitive cells. Here, we report the thermal transport properties of crystalline polythiophene with 28 atoms per primitive cell using an ab-initio approach that rigorously includes finite temperature anharmonicity and quantum nuclear effects. The calculated room temperature thermal conductivity is 176 Wm-1K-1, a high value that arises from exceptional phonon focusing along the chain for certain branches and despite short lifetimes in the picosecond range. Our finding suggests that many complex molecular crystals with stiff intra-chain bonds are intrinsically good thermal conductors as phonon focusing occurs in any crystal with anisotropic bonds.