Interplay between Phonons and Anisotropic Elasticity Drives Negative Thermal Expansion in PbTiO3

We use first-principles theory to show that the ingredients assumed to be essential to the occurrence of negative thermal expansion (NTE)—rigid unit phonon modes with negative Grüneisen parameters—are neither sufficient nor necessary for a material to undergo NTE. Instead, we find that NTE in PbTiO₃ involves a delicate interplay between the phonon properties of a material (Grüneisen parameters) and its anisotropic elasticity. These unique insights open new avenues in our fundamental understanding of the thermal properties of materials and in the search for NTE in new materials classes.